Both teams have made perfect starts to their respective seasons, collecting maximum points from their five league games so far while PSG have also lifted the Trophee des Champions.
The French outfit have been knocked out in the last 16 of this competition in each of the past two seasons, though, whereas Liverpool made it all the way to the final last term before being beaten by Real Madrid.
Make sure you don't miss a moment of the action courtesy of our minute-by-minute updates below.
OFFICIAL LINE-UPS
LIVERPOOL: Alisson; Alexander-Arnold, Van Dijk, Gomez, Robertson; Milner, Henderson, Wijnaldum; Salah, Sturridge, Mane
LIVERPOOL SUBS: Mignolet, Fabinho, Keita, Firmino, Moreno, Shaqiri, Matip
PSG: Areola; Meunier, Silva, Kimpembe, Bernat; Rabiot, Marquinhos, Di Maria; Mbappe, Cavani, Neymar
PSG SUBS: Kehrer, Choupo-Moting, Diarra, Draxler, Nkunku, Nsoki, Cibois
Liverpool make a statement in their opening match of the Champions League campaign with a 3-2 victory over a PSG side who were underwhelming and outplayed for long spells by the hosts.
Quickfire goals from Daniel Sturridge and James Milner gave Liverpool the lead in the first half, only for Thomas Meunier to halve the deficit just as quickly. It looked as though Liverpool might be punished for their profligacy when Mbappe tucked away an 83rd-minute equaliser, but Firmino came off the bench to fire home the winner in stoppage time, sending Anfield wild in the process. Thanks for joining our live coverage of the match!
90+4 min LIVERPOOL 3-2 PSG
90+3 min LIVERPOOL SUB: One final change late on for Liverpool as Fabinho comes on for his debut, replacing Mane.
90+2 min Surely that is the winner from Roberto Firmino, who shows that there is no problems with his vision by firing a pinpoint finish into the bottom corner!
Milner wins the ball off Mbappe just outside the PSG area and feeds it to Firmino, who twists and turns inside the box before drilling a fine effort across goal and into the corner.
90+2 min LIVERPOOL 3-2 PSG (ROBERTO FIRMINO)
90 min There will be three minutes of added time at the end of this match.
88 min PSG almost catch Liverpool on the break as Neymar's ball forward leaves the Reds exposed at the back. The ball drops to Draxler, who bides his time but sees his eventual effort blocked by Van Dijk.
87 min Mane wins a free kick just outside the area and Alexander-Arnold takes it, with his effort taking a slight nick off Rabiot before clipping the outside of the post.
85 min LIVERPOOL SUB That mistake will be Salah's last action of the match as he is replaced by Xherdan Shaqiri.
83 min Liverpool should have put this game to bed long ago, but they find themselves level here as Kylian Mbappe tucks away an equaliser at the death.
The Reds are trying to launch a counter, but for the second time in quick succession Salah gives the ball away carelessly. Neymar pounces on it and drives forward before being tackled by Van Dijk. The ball squirms to Mbappe inside the box, and he takes a touch before tucking it into the bottom corner.
83 min LIVERPOOL 2-2 PSG (KYLIAN MBAPPE)
82 min Lovely football from Liverpool again as Mane and Salah combine down the right channel. Mane sees his initial cross deflected, before picking it back up and dinking it over Kimpembe and firing an effort right across the face of goal.
80 min PSG SUBS: Double change for the visitors as Julian Draxler and Eric Maxim Choupo-Moting replace Cavani and Di Maria.
80 min Liverpool almost break as Salah flicks the ball into the path of Mane, who is only denied a one-on-one by the offside flag, which is incorrectly raised.
78 min PSG are seeing more of the ball now, but they are lacking a bit of urgency in their play despite the situation. Time is running out for the visitors!
76 min This has been a very underwhelming performance from PSG, but with the deficit still just one goal Liverpool remain vulnerable. The hosts could really do with a third here to set any nerves at ease.
74 min For all of their attacking quality - not to mention the fact that they are chasing the game - PSG are yet to have a shot on Liverpool's goal in this second half. Liverpool will kick themselves if they don't win this one.
72 min Decent chance for Liverpool as Van Dijk climbs highest inside the area to knock the ball down for Salah, but Marquinhos does just enough to put the winger off and force him to fire it wide.
72 min LIVERPOOL SUB: Liverpool make their first change of the evening as Roberto Firmino replaces Sturridge.
71 min Milner swings yet another corner into the box, but Cavani is there to flick it behind for one more corner. Still Liverpool looking the most likely to add to the scoring.
69 min Henderson wins the ball back in midfield again and launches another counter, but Sturridge takes too long to make a decision and eventually he and Henderson are crowded out.
67 min Liverpool win a free kick in a good position and Henderson chips it towards Alexander-Arnold on the right channel. It is a clever move, with Alexander-Arnold looking for Mane in the middle, but Silva is there to put it out.
65 min Waste of a decent attacking opening for Liverpool here as Sturridge tries his luck from the edge of the area, but fires it high and wide of the target.
64 min Liverpool will be confident that there are still more goals in this one for them. They are knocking the ball around nicely inside the PSG half, and in truth this has been a much easier game than they would have expected so far.
62 min Big chance for Liverpool to put that disallowed goal behind them and add a third, but Sturridge gets his header all wrong and it is easy for Areola in the end. That wasn't much harder than the header he scored in the first half.
60 min PSG have got away with one to a certain extent there, as both the referee and the linesman seemed to think it was a perfectly good goal. How big could that moment prove to be?
58 min Hugely controversial moment at Anfield as Liverpool think they have added a third goal, only for it to be disallowed very late!
Salah put the ball into the back of the net, but it is chalked off for a foul by Sturridge on Areola in the PSG goal. In retrospect it is probably the right decision, but it was a late call and seemed to come from the official behind the goal.
56 min Liverpool have seen the vast majority of possession in this second half so far, although with only a one-goal lead that could also be dangerous considering PSG's threat on the counter. The Reds look in control right now, though.
54 min Mbappe finally shows the first signs of his dazzling footwork, skipping away from Henderson and then past Robertson, but his final delivery does not match the buildup play.
52 min We have seen very little from Neymar, Cavani and Mbappe so far tonight, and huge credit for that must go to Liverpool's defence. They are keeping that deadly front three very quiet indeed.
50 min PSG come forward with pace, but Liverpool are quick to get back and quell the attack, which eventually comes to an end with Neymar being offside.
48 min The worry for Liverpool in this half will be that PSG do not play as poorly as they did in the first, although with Neymar, Mbappe and Cavani refusing to track back, they should still get penty of space to attack.
46 min PSG get us back underway for the start of this second half at Anfield!
Well, that opening 45 minutes certainly did not disappoint! Three goals in the space of 10 minutes give Liverpool a 2-1 lead over PSG at the halfway stage at Anfield, and I would be surprised if we have seen the last of the goals in this one.
Liverpool have been the better team so far and looked as though they might punish a lacklustre PSG performance until the visitors pulled one back.
45+1 min LIVERPOOL 2-1 PSG
45+1 min There will be a minimum of one minute added time at the end of this first half.
45+1 min Meunier goes into the book for a trip on Mane.
44 min Alexander-Arnold bursts down the right flank and clips a cross into the box, but Sturridge's touch sends the ball into the arms of Areola, who beats Mane to it.
44 min UPDATE: Atletico Madrid have come from behind against Monaco, with Diego Costa and Jose Gimenez getting on the scoresheet.
42 min That is three goals in the last 10 minutes now - this match was never going to disappoint, was it?! Liverpool will kick themselves if they do not go into the break ahead in this match, though.
40 min PSG are right back into this match as they halve the deficit through Thomas Meunier's instinctive finish!
Di Maria's initial cross into the box wasn't the best and Cavani missed with an attempted bicycle kick, but it then bounced off the leg of Robertson and fell to Meunier, who did not have a second thought before volleying it past Alisson and into the bottom corner.
40 min LIVERPOOL 2-1 PSG (THOMAS MEUNIER)
38 min Anfield is absolutely rocking here, and PSG don't seem to be able to react! Here is the goal which started it all off...
36 min Liverpool double their lead with less than 10 minutes remaining in the half as James Milner tucks his penalty into the bottom corner!
It is a mindless challenge from Bernat to give away the spot kick as he dangles a leg out to trip Wijnaldum, who had three other PSG defenders around him. There is no doubt that it is a penalty, and Milner makes no mistake by putting it beyond the reach of Areola!
36 min LIVERPOOL 2-0 PSG (JAMES MILNER, PEN)
35 min Penalty to Liverpool as Bernat trips Wijnaldum in the box!
34 min Big chance for PSG from the resulting corner as Liverpool's defence is asleep to Mbappe's peeling run. Neymar plays it along the floor and Mbappe really should score, but he fires it narrowly over.
34 min PSG respond by winning a free kick in a good position and Neymar goes for power from all of 30 yards out, but the Liverpool wall does its job.
32 min Liverpool almost make two in quick succession as Wijnaldum causes havoc with a late dart into the area. The ball drops to him with his back to goal, but his attempted shot around the corner is blocked.
30 min First blood goes to Liverpool in this heavyweight clash, and it is Daniel Sturridge who marks his first Champions League start for the club with a goal!
Robertson whips a beauty of a cross into the box after Alexander-Arnold's delivery went all the way through, and Sturridge has peeled off his man to thump a header past Areola!
30 min LIVERPOOL 1-0 PSG (DANIEL STURRIDGE)
29 min Liverpool get away with one here as Di Maria is given the time to float a pass over to Neymar, who finds himself clean through on goal. The linesman's flag goes up, but the replay shows that the Brazilian was actually on.
27 min Van Dijk is the first name in the book tonight for grabbing Mbappe to prevent him from racing clear.
26 min Mane collects the ball on the right flank and looks up to see Neymar defending against him. Mane subsequently beats Neymar with ease to advance into the area, but he slices his eventual effort well off target.
24 min Midway through this half now and it is still very finely poised between these two sides. Liverpool have been the better team so far, but PSG are growing into the game.
22 min UPDATE: There have been a couple of goal already in the 8pm Champions League kickoffs tonight, with Galatasaray leading Lokomotiv Moscow and Monaco breaking the deadlock against Atletico Madrid.
20 min PSG are beginning to grow into this game now, but Liverpool almost break free as a fine pass from Milner finds Mane. Areola finds himself in no-man's land, but Silva defends the situation really well to clean up the situation.
18 min PSG have a chance to break here as Mbappe tears down the right flank before trying to find Cavani or Neymar in the middle, but his pass is behind them both and a good counter-attacking chance goes begging.
17 min PSG finally come to life inside the Liverpool area as Neymar skips away from his marker before firing his effort straight at Alisson. The Liverpool keeper parries it out into a dangerous area, where Cavani is alive to it, but he cannot get enough on his rebound.
15 min Another sight of goal for Liverpool from their sixth corner of the match as Gomez does really well to get his head to a delivery that is behind him, but he cannot steer it on target.
15 min Half a chance for Liverpool from yet another corner - their sixth already - as Gomez does really well to get his head to a delivery which is behind him. He cannot steer it on target, though.
14 min Concern for Liverpool here as Mane goes down after a innocuous slide off the field with no PSG players around him. It looks like he will be fine to continue, though.
12 min This has been a really positive start from Liverpool, who have kept PSG under pressure from the majority of the game so far and are certainly winning the midfield battle at the moment.
10 min Henderson nicks the ball off the toe of Neymar to launch another counter, finding Salah who in turn picks out Mane. Mane finds space to shoot from just outside the area, but his effort is tame and easy for Areola.
10 min Again Salah puts it right under the crossbar and Areola this time is forced to tip it over his own crossbar.
8 min Salah comes across to take the corner and puts it right on top of Areola, who needs to punch it away. Moments later Salah and Wijnaldum team up to earn an attacking throw-in, and Anfield shows its appreciation.
7 min More good pressure from Liverpool as Areola is called into action again. This time it is Milner who goes for goal from just outside the area, but his low strike is tipped wide by the PSG keeper.
6 min This time Milner plays it short to Salah, who gives it straight back to Milner. The Liverpool midfielder advances into the box and to the byline before drilling a ball into the box which Van Dijk does well to steer on target. Areola has to be alert to tip it over the top.
5 min Alexander-Arnold floats a cross into the box which Silva needs to come across and deal with ahead of Mane, conceding a corner which results in a second in quick succession...
3 min PSG are seeing the vast majority of possession in these opening exchanges, and we have just seen the first glimpse of Neymar as he gets past Alexander-Arnold, Henderson, Mane and Milner before seeing his through-ball mopped up by Van Dijk.
1 min KICKOFF: Here we go, then! Anfield is rocking as Liverpool get us underway for this mouth-watering clash...
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