The match, played against the backdrop of Russia's invasion of Ukraine and Chelsea owner Roman Abramovich's decision to hand over stewardship of the club, was won in dramatic style as Chelsea boss Thomas Tuchel saw his late gamble backfire.
After 20 successful penalties, Caoimhin Kelleher was the Liverpool hero, first stepping up to make it 11-10 and then seeing Kepa Arrizabalaga smash his spot kick high over the bar to settle an extraordinary game.
Tuchel introduced Kepa in the 119th minute ahead of the shootout -- an intervention that brought back memories of the 2019 final when Kepa refused to be substituted by Maurizio Sarri ahead of the penalty shootout with Manchester City. Kepa prevailed in that standoff, only to see City win the shootout 4-3 to lift the cup. And once again the goalkeeper was on the losing side as Liverpool celebrated a remarkable victory.
"It's a mad one. I got close to a few when it came down to me I didn't even think I had scored the winning penalty. I'd forgotten I'd got the winning one. All the lads were class, I was just happy to score," Kelleher said.
Ahead of the final Chelsea released a statement on Sunday saying the situation in Ukraine was "horrific" while both sets of players stood and applauded in solidarity, with a message that read "Football stands together" before kickoff. The match itself was a gripping spectacle of chances at either end, a litany of disallowed goals and high drama, settled on penalties following a gruelling 120 minutes of football.
"Football can be a brilliant game and it was a brilliant game, no worries and no regrets," Tuchel said afterward."We gave everything and it was a brilliant match of football. The disallowed goal for Romelu [Lukaku] is a very close call -- there are bad feelings about this call.
"You need a bit of luck, we scored three times, had big chances, they had big chances, It was a fair result all the way to have a draw."
On Kepa's heartbreaking performance, Tuchel said: "It is unusual all 11 players need to shoot, he took it a bit too quick. Sometimes these things can turn against you but you make them when they need to be made, not after when people can judge you."
Liverpool's success means the club remain on for an unprecedented haul of four trophies this season, with Jurgen Klopp's side still in the FA Cup and Champions League as well as fighting Manchester City for the Premier League title. Success at Wembley represented Klopp's first domestic cup for Liverpool after winning the Champions League and Premier League title -- and the club's first League Cup win for 10 years.
"Even in professional football there should be space for some sentiment. Caoimhin Kelleher is a young boy, plays in all the competition, what do I do? I am two things, a professional manager and a human being and the human being won. He deserves it," Klopp said.
For Chelsea, Tuchel was unable to add to his collection of three trophies since taking over as manager last year and questions will be asked over his decision to replace the outstanding Edouard Mendy with Kepa, who failed to save a single penalty before hitting his spot kick high over the bar.
The match was defined by a succession of golden missed chances, fine goalkeeping displays and VAR controversy, with Mason Mount particularly culpable of two big misses in each half.
Klopp and Tuchel both had goalkeeping conundrums ahead of the game, with the Liverpool manager choosing to keep faith with 23-year-old Republic of Ireland international Kelleher ahead of first choice Alisson and his Chelsea counterpart opting for Blues No.1 Edouard Mendy instead of Kepa despite the world's most expensive goalkeeper playing in every round prior to the final. Tuchel also made the call to bench Romelu Lukaku.
Kai Havertz started in place of Lukaku and began brightly, with the ball finding its way to Christian Pulisic early on but Kelleher kept him out from close range when the United States forward should have done better.
Mendy then leapt into action 30 minutes in to execute a quite stunning double save, first to deny Naby Keita from range and then inexplicably keeping out Sadio Mane's powerful rebound from all of six yards out when he seemed destined to score.
Mount was the next to miss a gilt-edged opportunity when it seemed easier to score as he bounced a volley wide of the post with the goal at his mercy just before half time. Mount was guilty of another glaring miss four minutes into the second half when he found space unmarked in the box, but could only hit the post with Kelleher beaten.
Tuchel dropped to his knees in agony at the sight of Mount's miss and he was a relieved man on 64 minutes when Mendy's poor kick out gave Mohamed Salah a chance one on one, but his dink was cleared off the line by Thiago Silva.
He was even more relieved soon after when Joel Matip's header was ruled out after VAR ruled Virgil van Dijk was offside in the build up. Havertz then headed in with 13 minutes to go but this time, no VAR was needed to rule substitute Timo Werner was offside.
Van Dijk and substitute Lukaku both brought good saves from the respective keepers in injury time in normal time, before Lukaku had the ball in the net seven minutes into extra time, only for VAR to rule him offside.
Havertz had a goal of his own ruled out for offside in the second half of extra time before more drama unfolded in the shootout as Liverpool held their nerve and Kepa lost his.
"It was amazing, very special to win trophies at this football club. Always difficult when it goes to penalties," Liverpool captain Jordan Henderson told Sky Sports. "We have used all the squad, academy, first team, all chipped in which makes it really special.
"It is mad to think it was 10 years we won it. Today was really special, never take for granted playing for this club. The fans deserve it and hopefully it can give us a kick start for the rest of the season."