A frenzied start in which the Reds sought to swarm their opponents was punctured in minute 12 as Ousmane Dembele was able to net a goal that equalised the aggregate score to 1-1.
Both sides carved out multiple chances to tip the balance of the last-16 tie in their favour but they remained locked together throughout the remainder of the 90 and extra-time, forcing penalties.
Visiting goalkeeper Gianluigi Donnarumma denied both Darwin Nunez and Curtis Jones from the spot and PSG prevailed 4-1 to advance.
Team
There were three changes by head coach Arne Slot, who brought Diogo Jota, Alexis Mac Allister and Andy Robertson back in to his starting XI.
Cody Gakpo was able to return and take a place among the substitutes.
Liverpool: Alisson, Van Dijk, Konate (Endo, 111), Diaz (Gakpo, 101), Szoboszlai (Elliott, 106), Mac Allister (Jones, 91), Salah, Jota (Nunez, 73), Robertson, Gravenberch, Alexander-Arnold (Quansah, 73).
Unused subs: Jaros, Kelleher, Chiesa, Tsimikas, McConnell.
First half
The noise inside Anfield was ferocious by the time the game kicked off and Liverpool’s intensity – turned around to attack towards the Kop – matched the atmosphere.
Amid the fervour, the Reds were able to produce a marvellous move within four minutes that so nearly produced an opening goal.
Dominik Szoboszlai deftly chested down a forward pass and fed the ball back to Mac Allister, who sweetly surged into the area with a first touch that left his marker frozen.
The Argentinian dragged a low cross to Mohamed Salah at the far post and his finish was on course for the target until Nuno Mendes got a vital touch to deflect it over.
Salah swiftly had another attempt at goal that he curled wide having burst into the position from near halfway, and Virgil van Dijk then saw a downward header halted on its route to goal from a Mac Allister corner delivery.
The flow of play suggested a goal was coming for the hosts, but on 12 minutes PSG pounced to level up the aggregate score.
Dembele dropped deep to take possession and sweep it out right before diverting his run into the area. When the cross aimed back to him arrived, Ibrahima Konate’s effort to touch it away instead left Alisson Becker helpless and allowed the PSG forward to tap in to an exposed net.
As the respective bosses had foreseen, it was a match of immense quality – and chances were frequent.
Donnarumma got gloves on a creeping, low Konate strike from outside the box, Alisson foiled a weak Bradley Barcola finish after he was threaded in by Khvicha Kvaratskhelia, and Jota flicked a header too high.
A heavy Dembele touch gave Alisson the chance to smother a dangerous one-v-one from another PSG turnover, and Kvaratskhelia whipped a shot just over the bar as the visitors continued to pose significant threat.
A Dembele curler flicked off Mac Allister and looped just wide of the goalframe before half-time landed with the tie all square.
Second half
Liverpool were on the front foot from the restart and had the ball in the net on 53 minutes – but ultimately to no avail.
After Donnarumma had repelled a Trent Alexander-Arnold blast, the No.66’s low follow-up bounced off the right post, along the line and away.
He squared the next rebound for Szoboszlai to convert from close range. Celebrations were all too brief, though – the flag was raised for a Luis Diaz offside much earlier in the move.
Willian Pacho made a brilliant block to deny Szoboszlai and Donnarumma then clawed out Diaz’s deflected header as the Reds pressed ever more strongly to regain the advantage.
Slot lost Alexander-Arnold to an injury as the game ticked towards its final quarter-hour of normal time, and the Dutchman also deployed Nunez in place of Jota in central attack.
Simultaneously, the tempo of the Reds’ play was beginning to be better managed by PSG, but the hosts went close once more on 79 minutes.
Robertson’s set-piece hoist from deep reached an unmarked Jarell Quansah – the Alexander-Arnold replacement at right-back – and his stooping header across Donnarumma hit the inside of the far post and stayed out.
Kvaratskhelia swiped one into the Kop as the visitors almost snatched the tie before the end of normal time that arrived with still nothing to separate the teams.
Extra-time and penalties
The additional half-hour began with two sights of goal for PSG, with Lucas Beraldo nudging a header a yard wide of the left post just two minutes in.
Fellow substitute Desire Doue then spun inside the box and whistled an effort even more narrowly the wrong side of the same bit of woodwork.
Liverpool ended the first period in the ascendancy and the introduction of Gakpo was followed after the change of ends by Harvey Elliott as Slot tried to find the way through.
Alisson and Dembele recommenced their duel when the Frenchman was teed up to the left of goal and aimed a side-footer that the Reds’ No.1 scooped away.
Konate had to limp off as the clock showed 111 minutes played, Wataru Endo called on to take the defender’s spot alongside Van Dijk at the back.
The aggregate deadlock continued and penalties would have to settle the berth in the quarter-finals.
PSG were on target with each of the four they attempted and Donnarumma’s saves from Nunez and Jones meant it was the Ligue 1 side who moved forward to the next round.
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