Mohamed Salah's late goal gave Liverpool the lead before Darwin Nunez's stoppage-time sealer secured a 2-0 win over Napoli to give Jurgen Klopp victory in his 400th game in charge, ending the visitors' unbeaten start to the campaign.
Both sides were already assured of a place in the knockout stages of the competition, with only a four-goal winning margin enough to see Liverpool usurp Napoli in top spot.
The Reds managed two late strikes courtesy of Salah and Nunez, with Salah scrambling one over the line in the 85th minute after Alex Meret just about kept out substitute Nunez's header.
Nunez added a second from the final act of the match as Napoli, who earlier had a Leo Skiri Ostigard effort ruled out for offside, saw their unbeaten run ended at 17 matches.
Neither team could really find any rhythm in a quiet first half that took half an hour for the first shot on target to arrive, with Tanguy Ndombele forcing a save out of Alisson.
Liverpool attacked up the other end and only an Meret stop prevented Thiago Alcantara from opening the scoring, shortly before Curtis Jones headed just over the crossbar.
Ostigard guided Khvicha Kvaratskhelia's free-kick delivery past Alisson eight minutes into the second period, but VAR – after a three-minute wait – ruled the defender was offside.
Kvaratskhelia then had a powerful volley saved by Alisson as Napoli, who had won their previous five group outings with a competition-high 20 goals, pushed for a winner.
A winner did arrive, albeit at the other end as Meret prevented Nunez's header from crossing the line, but Salah was there on the follow-up to poke over the line.
Nunez, introduced in the 73rd minute, added further gloss to the scoreline when tapping in a saved Virgil van Dijk header from under the bar.
What does it mean? Victory for Klopp on milestone occasion
Liverpool did not win by the four-goal margin required, which was never likely against in-form Napoli, meaning they will be unseeded in Monday's draw for the last 16.
But the Reds at least manage to put Saturday's league loss to Leeds United behind them with a narrow, if arguably slightly undeserved, victory in Klopp's 400th match in charge.
It was also the German's 100th Champions League game in his career, making him the seventh manager to reach that figure.
Darwin's chaotic cameo
Nunez has gained a reputation of being an 'agent of chaos' because of his erratic playing style, and so that proved in his 20 minutes or so on the field against Napoli.
He played a big part in the opening goal and then added a late second, albeit after a nervy VAR check, for what was his first Liverpool goal in the Champions League.
Spalletti's side thwarted
Napoli had won 13 games in a row entering this match, including five from five in the Champions League with 20 goals scored – four short of Bayern Munich's all-time record.
The Serie A leaders managed just two shots on target and accumulated an expected goals (xG) value of 0.43, with this going down as an off-day for Luciano Spalletti's talented side.
What's next?
Liverpool will look to reignite their Premier League campaign when they travel to Tottenham on Sunday, while Serie A leaders Napoli head to second-place Atalanta on Saturday.
Borussia Dortmund receive injury boosts ahead of Champions League semi-final
Borussia Dortmund midfielder Marcel Sabitzer and forward Donyell Malen are likely to be fit in time for Wednesday's Champions League semi-final first leg at home against Paris Saint-Germain, coach Edin Terzic said on Tuesday.
Dortmund will also have Emre Can and Ian Maatsen back from suspension, while Sabitzer, who was out ill for several days, and Dutch international Malen, recovering from an injury picked up during the March international break, have returned to training.
"Marcel and Donyell both took part in training. We expect that they will be at our disposal tomorrow," said Terzic.
"Marcel is feeling better, and we need him in his form from before his illness tomorrow."
Dortmund have struggled in the league this season and on Saturday suffered a crushing 4-1 loss to direct rivals RB Leipzig, who held on to fourth place, leaving them in fifth with three matches remaining.
The top four teams qualify for the Champions League group stage next season.
Germany is likely to earn a fifth spot as one of the top two in UEFA's coefficient table depending on the remaining results in European competition this season.
Dortmund's deep Champions League run this season, however, has kept fans hopeful of some silverware.
The sides also met in the group stage, with the French side winning 2-0 in Paris before a 1-1 draw in Dortmund.
"You could sense in the return leg that we had learned the lessons from the first game," Terzic said.
"Now PSG look to be at their very peak this season with only one defeat in 2024 and a good run of results. We will have to show an improved performance from that in Dortmund."
"We are confident that will show it tomorrow and next week in Paris. The clear goal is to gain a small advantage after the game tomorrow. We know we have to play at least 180 minutes at the highest level to have any shot at our dream."
Preston 0-3 Leicester City: Foxes seal Championship title in style
Leicester City cruised to a 3-0 win over Preston in the Championship on Monday to clinch the title with a game to spare.
Jamie Vardy was the star for the Foxes as he scored in both halves before Kasey McAteer made sure of the points with an unmarked header.
Abdul Fatawu had the chance to cap an already memorable night for the travelling fans but hit the post with his curler.
Preston slumped to a fourth consecutive defeat, while Leicester go into their final game against Blackburn Rovers with the knowledge that they will lift the trophy after the final whistle.
Data Debrief
Jamie Vardy has scored 18 goals this season (two in this game), more than any other Leicester player in the competition. He has also netted in his last three games, scoring four goals in total.
It was a dominant performance from the Foxes, who had 19 shots with 11 of those on target. At the other end, Preston only managed to test Jakub Stolarczyk once from their five attempts.
Recruitment crucial if Slot gets Liverpool job, warns Brands
Arne Slot must only settle for the best in the transfer market if he succeeds Jurgen Klopp as Liverpool manager at the end of the season.
That is the view of PSV president Marcel Brands, who has warned Slot against taking several Eredivisie players with him in comments which might be interpreted as a dig at Manchester United boss Erik ten Hag.
Liverpool are reportedly close to reaching an agreement with Feyenoord to appoint Slot, who led the Rotterdam giants to just their second league title this century in 2022-23.
Should Slot get the job, he will be taking over at what could be a time of great upheaval at Anfield.
Star forward Mohamed Salah could follow Klopp through the exit door as he enters the final 12 months of his contract, with renewed interest from the Saudi Pro League likely.
The Egyptian was involved in a public spat with Klopp during Saturday's 2-2 draw with West Ham and has only scored three Premier League goals since going to the Africa Cup of Nations in January.
Asked how Slot should approach taking over during a time of transition, Brands told Goedemorgen Eredivisie: "Don't focus blindly on signing five Dutch players.
"He has to look very carefully at what he needs with his style of football, and only settle for top players."
Brands' comments come as Slot's fellow Dutchman Ten Hag continues to attract fierce criticism amid an underwhelming second campaign at Old Trafford, with Eredivisie recruits Antony, Tyrell Malacia and Lisandro Martinez having limited impacts this term.
Brands has warned Slot the pressure awaiting him at Anfield will match that Ten Hag has faced at United, saying: "Slot will be working at one of the biggest clubs in England.
"You have to realise that. Liverpool have supporters from all over the world, and the pressure is always there.
"Just like Manchester United, they really are the biggest clubs in England, but it is a fantastic challenge."
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