Both sides could claim to have been deserving winners in a classic free-flowing encounter full of goalscoring chances, remarkable saves and disallowed goals.
Even in the penalty shoot-out the two sides were inseparable with 21 successful kicks ratcheting up the tension.
It came down to a test between two goalkeepers with Liverpool's Caoimhin Kelleher belting his effort past Kepa Arrizabalaga who had replaced Edouard Mendy for the shoot-out.
Spaniard Arrizabalaga then blazed his effort over the bar into the massed ranks of Liverpool supporters who celebrated the club's first domestic Cup silverware for a decade.
While Liverpool manager Juergen Klopp had won the Premier League and Champions League since arriving at Anfield, it was a rare cup success for the German who had won only two of his previous eight finals with Borussia Dortmund and Liverpool.
For Chelsea manager Thomas Tuchel it meant his hopes of a fourth trophy in just over a year at Stamford Bridge fell just short. He won the Champions League last season and the European SuperCup and FIFA Club World Cup this season.
Chelsea, bidding to win a sixth League Cup, might well feel aggrieved after having arguably the better chances.
They almost took the lead early on when Cesar Azpilicueta played in a low pass to the unmarked Christian Pulisic whose first-time shot from six metres was kept out by Kelleher, who retained his place ahead of Alisson.
Chelsea were sharper in the early exchanges but were fortunate in the 17th minute when Sadio Mane got his angles all wrong with a header from Trent Alexander-Arnold's cross.
Liverpool grew into the game and Chelsea were indebted to a stunning double save by Mendy, first keeping out Naby Keita's low strike from the edge of the area and then springing across to deflect Mane's follow-up over the bar.
An absorbing first half ended with Chelsea threatening again, with Mason Mount volleying wide from a Kai Havertz cross.
Three minutes after the break Mount was presented with an even better chance when he chested down a dinked-through ball by Havertz but his shot rebounded off the inside of the post, leaving Tuchel beating the ground in frustration.
Liverpool responded just past the hour when Mohamed Salah was played clean through but his chip over Mendy lacked weight and Thiago Silva cleared the ball off the line.
Joel Matip thought he had put Liverpool ahead when he nodded in after Mane's header bounced up but, as the fans let off red flares, the goal was disallowed by referee Stuart Attwell after checking a pitchside monitor.
The cut and thrust continued with Salah again denied by Mendy before Chelsea had a goal chalked off for offside after substitutes Romelu Lukaku and Timo Werner combined to set up Havertz to force a header past Kelleher.
Even in the six minutes of stoppage time both sides were still throwing punches, with Mendy keeping out Virgil van Dijk's thumping header before Werner squandered a chance.
Lukaku then had a goal disallowed after cutting in from the right and drilling a shot past Kelleher, and Havertz had the ball in the net for a second time, only for another offside decision to go against the German.
Arrizabalaga was sent on by Tuchel at the end of extra time for the penalties but instead of becoming a hero, he handed the trophy to Liverpool.