Jurgen Klopp’s injury-hit side finished a gruelling clash with a host of raw youngsters on the pitch, but it was their experienced captain who clinched the club’s 10th League Cup triumph.
Van Dijk earlier had a goal controversially disallowed by VAR, but the Dutch defender pounced to nod home with just two minutes left.
It was Liverpool’s first trophy following Klopp’s bombshell announcement that he will step down at the end of this season.
« What happened here today is absolutely insane. These things are not possible besides a team, squad, academy full of character, » Klopp said.
« The craziest thing is we deserved it. I couldn’t be prouder of them. Wow! It was really cool.
« I’m sure we brought on all the kids! We needed fresh legs. They were very young, but they did the job. »
Klopp has now won seven major trophies in his nine-year Anfield reign.
The German will hope Liverpool’s first silverware since the 2022 FA Cup will be the springboard for an incredible farewell tour.
Quadruple-chasing Liverpool sit top of the Premier League, face Southampton in the FA Cup fifth round on Wednesday and take on Sparta Prague in the Europa League last 16.
It was another bitter Wembley experience for Chelsea, who lost the 2022 League Cup and FA Cup finals against Liverpool.
Blues boss Mauricio Pochettino has asked Chelsea fans not to judge him on « winning titles » in the midst of a troubled first season in charge.
But Chelsea remain without domestic silverware since the 2018 FA Cup and had only themselves to blame after missing a host of chances in normal time.
« That was the key. We created four, five or six big chances and we didn’t score. In a game like this, whoever scores first will have a big advantage, » said Pochettino, who is still to win a trophy in English football.
« We felt the disappointment of not winning in normal time. We didn’t have the energy in extra-time. They scored in the last minutes and it was difficult to react. »
Ravaged by injuries to 11 players, Liverpool’s list of star absentees included Mohamed Salah, Trent Alexander-Arnold, Alisson Becker, Darwin Nunez, Diogo Jota and Dominik Szoboszlai.
That meant starts for 20-year-olds Conor Bradley and Harvey Elliott, while Bobby Clark (19), James McConnell (19), Jarell Quansah (21) and Jayden Danns (18) all came off the bench.
– Goals ruled out –
Despite their youthful line-up, Liverpool settled quickly as Luis Diaz led the charge.
Taking advantage of Chelsea’s hesitant defending, Diaz advanced into the area for a fierce strike that forced a good save from Djordje Petrovic.
Against the run of play, Chelsea should have taken the lead with their first incisive raid.
Conor Gallagher’s cross deflected to Cole Palmer just six yards out, but his strike produced a superb save from Caoimhin Kelleher.
Ryan Gravenberch joined Liverpool’s ever-growing injury list when he was stretchered off after the midfielder’s leg twisted awkwardly in a challenge with Moises Caicedo.
Liverpool looked to have broken the deadlock on the hour when Van Dijk climbed above Ben Chilwell to head in Andrew Robertson’s free-kick.
But VAR intervened, prompting referee Chris Kavanagh to disallow the goal for offside against Wataru Endo, who blocked Levi Colwill from marking the Dutch defender.
Chelsea were left to rue Axel Disasi missing a sitter and Gallagher hitting the post before taking a heavy touch that allowed Kelleher to save.
In a pulsating finale, Kelleher made saves from Palmer and Christopher Nkunku to force extra-time.
Danns almost guided his header over Petrovic and Elliott was inches away when he volleyed against the post.
Liverpool would not be denied and with penalties just two minutes away, Van Dijk met Kostas Tsimikas’s corner with a header that flashed past Petrovic as Klopp raised his arms with a smile that bordered on disbelief.
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© Agence France-Presse