The former West Ham goalkeeper, starting in place of the injured Alisson Becker, saved Tammy Abraham’s spot-kick after nine perfect efforts previously.
The two sides could not be separated after 120 minutes of football, with the score level at 2-2, and the Reds eventually came out on top.
After such a taxing tie in humid conditions in Turkey, they now have to quickly switch their attentions to Saturday’s Premier League trip to Southampton.
Manager Jurgen Klopp praised the part played by Adrian, the Liverpool manager adding: “It’s so nice for him. I don’t think he won a lot in his life so to win this big one is so nice for him.”
The Liverpool manager paused his TV interview to call out the keeper’s name and referenced a scene from the hit film Rocky.
Klopp shouted: “Adrian. It’s like in Rocky.”
The Liverpool boss added: “It’s about winning it and we did that at the end. We showed character, Chelsea showed character as well. I think nobody in the stadium wanted twice 15 minutes (in extra time), it was a real killer.”
Olivier Giroud gave the Blues a deserved first-half lead after a fine through-ball from summer addition Christian Pulisic.
The USA international, who signed permanently at Stamford Bridge in January before returning on loan to Borussia Dortmund, then hit the back of the net before half-time but it was ruled out for offside by Stephanie Frappart, who made history on the night after becoming the first woman to referee a major men’s UEFA match.
Jurgen Klopp introduced Roberto Firmino at the break and the Brazilian made an immediate impact, setting up Sadio Mane to draw them level.
The Senegal international was starting his first match since returning late from his summer break due to international duty.
As the game entered extra-time, he doubled his tally, Firmino again the provider as he opened up his body and finished brilliantly into the top corner.
Frank Lampard’s side were back on level terms six minutes later as Adrian brought down Tammy Abraham in the box and Jorginho stepped up to coolly convert the resulting penalty.
After further extra-time, the game was to be decided by penalties. The first nine all found the back of the net, before Abraham was denied by Adrian.
- Only Barcelona and AC Milan (5) have won the UEFA Super Cup more often than Liverpool (4).
- Chelsea have now been runners-up in three consecutive UEFA Super Cup appearances (2012, 2013 and 2019) – only Barcelona and Sevilla (4 each) have been runners-up on more occasions.
- This was the 11th match between Liverpool and Chelsea in European competition, making it the most played European fixture between two sides from the same nation.
- With the scores level at 1-1 after 90 minutes, this was the fifth time in the last seven seasons that the UEFA Super Cup has gone to extra time or penalties.
- Liverpool became the first Premier League club to be involved in two penalty shootouts in the same month since Middlesbrough in February 2007.
- Olivier Giroud has scored 12 goals in 16 appearances in European competition for Chelsea, compared to just seven goals in 49 domestic games for the Blues.
- Liverpool’s Sadio Mané became the first African player to score in the UEFA Super Cup since Frederic Kanoute for Sevilla vs Barcelona in 2006.