Goals from Sadio Mane (2) for Liverpool and Olivier Giroud and Jorginho for Chelsea saw the game go to a shootout after a gruelling 120 minutes of action.
Liverpool went first and scored five out of five penalties, with Chelsea scoring all four of theirs to put the pressure on Tammy Abraham.
But the 21-year-old saw his shot saved by Adrian, who became an instant hero just nine days after joining Liverpool as a free agent.
Adrian grabbed the headlines for his save - and rightly so - but there was one player whose superb performance flew under the radar as a result: Joel Matip.
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The 28-year-old was undeservedly dropped in favour of Joe Gomez for last Friday's Premier League opener against Norwich City, which sparked fury amongst fans.
He was reinstated to face Chelsea in the UEFA Super Cup and repaid Jurgen Klopp's faith with a solid display alongside Virgil van Dijk.
Matip's long limbs make him a rather unorthodox centre-back, but he's deceivingly fast and capable of starting attacks with his marauding runs forward.
Liverpool fans have grown to love the Cameroonian and he's had them in stitches over the past few days with his celebrations as they lifted the trophy in Istanbul.
In the video below, Matip towers above everyone at the back and seems more than happy to just celebrate on his own, jumping up and down and throwing his arms in the air.
"JOEL MATIP, LIVERPOOL LEGEND"
LIVERPOOL FANS REACT
It's easy to see why Liverpool fans have warmed to Matip, who arguably deserves to keep his place at centre-back instead of Gomez.
Gomez had a poor game against Norwich and looked shaky at right-back in the UEFA Super Cup, so Klopp has some decisions to make.News Now - Sport News