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 Alex 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 Virgil van Dijk's goal-bound header from under the bar.
'One game at a time', says calm Slot after Leverkusen thrashing
Arne Slot insisted he will continue to look at "one game at a time" after leading Liverpool to a 4-1 victory over Bayer Leverkusen in the Champions League on Tuesday.
Luis Diaz's second-half hat-trick along with Cody Gakpo's 63rd-minute strike spoiled Xabi Alonso's Anfield return, moving the Reds top of the 36-team standings.
Liverpool have now won all four of their Champions League games under Slot. It’s only the second time that they have won all four opening games in a single season.
The Reds are now top of both the Premier League and Champions League, though Slot was keen to focus on the next task, which comes in the shape of Aston Villa on Saturday.
"I don't know if it was that much to do with intensity, but we took more risk," Slot said.
"They overloaded the midfield a lot, and we adjusted at half-time and took the risk to play one v one all over. We had better chances in the first half and they weren't a goal threat.
"As much as this time, how good they are in Europe, sometimes a strong target man is better than someone a bit faster.
"Curtis Jones did an incredible pass, and then you have someone with the pace of Lucho to finish it off. The pass was as good as the goal, in my opinion.
"You don't look ahead as a manager in the next three months. You're always one game at a time. We've got Aston Villa on Saturday, another tough game."
Diaz's treble saw him become only the second Colombian player to score a hat-trick in the Champions League, after Faustino Asprilla for Newcastle against Barcelona in 1997.
And he insisted that things have started brightly for Slot at Anfield, but said his team-mates must continue to perform to have something to show for it at the end of the season.
"The most important thing is the three points in this edition of the Champions League so we can keep progressing in the competition," Diaz said.
"Things have gone so well with the new manager, it wasn't easy for him to come in and fill Jurgen Klopp's shoes.
"Hopefully, we'll have something to show for it at the end of the season.
"We have top-quality players all over the pitch and I really enjoyed playing in that position today. I'm just happy to be on the pitch.
"I need to go and find that ball now because I need to keep it somewhere special at home."
For Alonso and Leverkusen, meanwhile, it marked a first Champions League defeat since 2022, while also conceding four or more goals in an away match in the competition since 2013 against Manchester United.
"It's painful the result more than the performance, probably," Alonso told Amazon Prime.
"But this is the Champions League, this is the highest level, and today it wasn't enough for us."
"It's too early to tell, but I can see that Liverpool have a very good balance, a very complete team.
"They work with 11 players, and they have the power to hold a clean sheet, which is important in the Champions League.
"In the Premier League, let's see. It's early to tell but it's looking good."
Alonso, who won the Champions League with Liverpool in 2005, was serenaded by the home supporters at Anfield during the contest.
"I tried to separate the game and the pain from the result from the nice feelings to come back. I'm really happy and thankful for that reception," he added.
Liverpool 4-0 Leverkusen: Diaz nets second-half hat-trick to extend 100% start
Luis Diaz scored a second-half hat-trick for Liverpool in their 4-0 victory at home to Bayer Leverkusen as they maintained their 100% start to their Champions League campaign.
Arne Slot's side lead the 36-team league within Europe's main competition following the result, with only Aston Villa alongside them as the only other club to have won every game. They play Club Brugge on Wednesday in their fourth match.
Back in Liverpool, things got off to a slow start with the scores level until the 61st minute. Diaz lifted the ball over goalkeeper Lukas Hradecky to get things moving before Cody Gakpo made it two just two minutes later.
Gakpo's goal was initially ruled offside by the on-field official, though was overturned following a VAR review.
Diaz then scored his second and Liverpool's third of the night in the 83rd minute after picking up Mohamed Salah's cross and slotting past Hradecky. The Colombian rounded things off deep into stoppage time with a tap in from close range.
The result leaves Leverkusen 11th in the table with seven points, having tasted their first defeat of the competition at Anfield.
Data debrief: Slot has Liverpool purring
Liverpool are now top of both the Champions League standings and the Premier League and continue to go from strength to strength under Slot.
They looked much more threatening in the second half compared to the first, registering 3.48 xG in the second period after just 0.64 in the first half.
Diaz, meanwhile, has now scored nine goals in 15 matches in all competitions.
Al-Nassr 5-1 Al-Ain: Ronaldo on target in AFC Champions League win
Cristiano Ronaldo powered Al-Nassr to a convincing 5-1 triumph over Asian Champions League Elite holders Al-Ain on Tuesday.
The victory carried a sense of redemption for Al-Nassr as they avenged last season's semi-final defeat to the same opposition on their way to lifting a second title in the competition.
Talisca fired the hosts into a fifth minute lead with a well-taken effort from the edge of the box before Ronaldo poked home his 908th career goal just after the half-hour mark.
Visiting defender Fabio Cardoso then deflected Angelo's effort beyond Khalid Eisa to hand Al-Nassr a comfortable advantage at the interval.
Al-Ain did, however, pull one back early in the second half when Park Yong-woo's strike struck the post and went in off the back of Al-Nassr goalkeeper Bento.
But the result was put beyond doubt late on when Wesley curled home Al-Nassr's fourth, before Talisca notched his brace in second half stoppage time.
Data Debrief: Return of Ronaldo
After winning five Champions League across his glittering career, Ronaldo is now eyeing a first AFC Champions League crown with Al-Nassr.
The 39-year-old has six goals in eight appearances in the competition, with his goal against Al-Ain ending a three-game goal drought for Al-Nassr.
Ronaldo also registered a team-high expected goals (xG) tally of 1.25 towards Al-Nassr's 2.67 total, while also producing more shots (eight) and touches in the opposition box (nine) than any other player on the pitch.
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