While Chelsea entered this match aiming to kickstart Mauricio Pochettino’s tenure, Liverpool were hoping that it would provide the first silverware of a trophy-laden swansong season for Klopp.
There was a nervy start with so much at stake, but the Reds settled into the occasion quicker and saw a looping Luis Díaz header saved by Đorđe Petrović, before the goalkeeper denied Díaz again following a slip from Axel Disasi.
Caoimhín Kelleher was then called into action in the 20th minute despite Liverpool’s dominance, making a superb save to stop Cole Palmer’s effort before Wataru Endō prevented Nicolas Jackson from getting off a follow-up.
Even with the scores remaining level, Klopp was soon left furious as Ryan Gravenberch was forced off in the 28th minute following a challenge from Moisés Caicedo.
Chelsea were then left bitterly disappointed, as Jackson raced behind to latch onto Palmer’s pass and tee up Raheem Sterling for a simple finish but had strayed offside by the finest of margins.
That offered a sign of the Blues’ improvements, although they were dealt further scares before the break as Cody Gakpo headed onto the post and Levi Colwill blocked Conor Bradley’s attempt.
There was plenty of intent in the second period and Van Dijk thought he had headed his side into the lead on the hour mark.
It was Liverpool’s turn to have their celebrations halted, though, as the goal was ruled out due to Endō blocking off Colwill after being in an offside position.
Conor Gallagher had three big opportunities to win the match, but hit the post, saw Kelleher rush out to deny him and then sent another attempt off-target.
A winner remained agonisingly out of reach as Christopher Nkunku sent the ball into Kelleher’s grateful clutches after it had pinballed in Liverpool’s box during added time.
That saw the sides remain level after 90 minutes for the eighth time in their last nine H2Hs, and the game had seemed destined for penalties after Petrović impressively saved headers from Jayden Danns and Harvey Elliott.
The youthful Reds were put into the lead by the experienced head of Van Dijk in the final moments, though, as Liverpool extended their record of EFL Cup victories by becoming the first club in history to win this competition 10 times.
The Reds also inflicted Chelsea’s sixth consecutive cup final defeat at Wembley - three of which have come against Klopp’s side.
Flashscore Man of the Match: Virgil van Dijk (Liverpool)
