Liverpool, the runners-up in the previous year's final, qualified directly for the group stage as the fourth-placed team in the Premier League. They were drawn into Group C alongside French champions Paris Saint-Germain, Napoli of Italy and Serbian champions Red Star Belgrade, who qualified through the play-off round and were making their Champions League group stage debut.

In the opening match of the group stage, Liverpool faced Paris Saint-Germain at Anfield and won 3–2 with a goal in stoppage time by substitute Roberto Firmino. Liverpool failed to produce a shot on target during their 1–0 loss to Napoli at the Stadio San Paolo on matchday 2, which the home side won with a 90th-minute goal from Lorenzo Insigne. Liverpool retook their position at the top of Group C following a 4–0 home victory over Red Star Belgrade on 24 October, including a brace from Mohamed Salah, but suffered a shock 2–0 defeat to Red Star two weeks later in Belgrade and fell to second place behind Napoli.

At the Parc des Princes in Paris, Liverpool were defeated 2–1 by Paris Saint-Germain and fell to third place in the group, putting them in jeopardy of a group stage elimination. Liverpool won their final group stage match, played on 11 December against Napoli at Anfield, with a goal by Salah and several saves by goalkeeper Alisson to preserve a clean sheet. Liverpool remained tied with Napoli on points, head-to-head record and goal difference but advanced to the knockout phase on total goals scored, with nine goals to Napoli's seven.

Liverpool were matched against German champions Bayern Munich in the round of 16 and played to a scoreless draw in the first leg at Anfield, mirroring the two sides' semi-final tie in the 1980–81 European Cup. They advanced to the quarter-finals by defeating Bayern 3–1 in the second leg at the Allianz Arena, with two goals from Sadio Mané and one from Virgil van Dijk in the second half. Liverpool won their quarter-final tie against Portuguese club Porto with an aggregate score of 6–1, winning 2–0 in the first leg at home and 4–1 away at the Estádio do Dragão.

In the semi-finals, Liverpool faced tournament favourites Barcelona. Former Liverpool forwards Luis Suárez and Philippe Coutinho were playing against their old club for the first time competitively since being sold to Barça for record transfer fees in 2014 and 2018, respectively. Barcelona took advantage of several missed chances from Liverpool's strikers and won 3–0 at home, with two second-half goals by Lionel Messi, including a 25-yard (23 m) free kick in the 82nd minute, his 600th goal for the club. With a three-goal deficit going into the second leg and preoccupation with winning the Premier League, Liverpool manager Jürgen Klopp asked his players to "just try" or "fail in the most beautiful way". Despite Mohamed Salah and Roberto Firmino being absent with injuries, Liverpool overturned the deficit with a 4–0 win at Anfield, advancing to the final 4–3 on aggregate, in what was described as one of the greatest comebacks in Champions League history. Liverpool's reserve striker Divock Origi scored the opening goal in the seventh minute, followed by a pair of goals in quick succession by half-time substitute Georginio Wijnaldum to level the tie on aggregate in the 56th minute. Alisson made a series of key saves to deny Barcelona a valuable away goal, a repeat of his performance for Roma in the previous year's quarter-final as they overcame a three-goal deficit against Barcelona. Origi scored the match's final goal in the 79th minute, taking advantage of a quickly-taken corner kick from Trent Alexander-Arnold that left him unmarked in the penalty area.

Liverpool won the final 2–0 against Tottenham in Madrid, with a penalty which was converted after 106 seconds by Mohamed Salah and a strike by substitute Divock Origi after 87 minutes.

 

1. Trent Alexander-Arnold

2. Alisson Becker

3. Joel Gomez

4. Andrew Robertson

5. Dejan Lovren

6. Joël Matip

7. Virgil van Dijk

8. James Milner

9. Jordan Henderson

10. Fabinho

11. Naby Keïta

12. Georginio Wijnaldum

13. Mohamed Salah

14. Roberto Firmino

15. Divock Origi

16. Sadio Mané

17. Xherdan Shaqiri

18. Daniel Sturridge

19. Jürgen Klopp

20. European Cup

 

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