The all-Premier League tie finished 1-1 after 90 minutes, with Liverpool eventually winning the shoot-out 6-5.
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Chelsea took the lead when forward Morgan Rogers converted from the penalty spot in the 40th minute. Liverpool equalised three minutes later through Cody Gakpo, who also scored with a penalty.
The match was contested by sides managed by childhood friends Xabi Alonso and Andoni Iraola, with Iraola’s team emerging victorious.
Liverpool’s advantage in the shoot-out was secured after Chelsea defender Wesley Fofana failed to produce a convincing penalty. Liverpool defender Joe Gomez had converted his attempt, while Kostas Tsimikas and Emmanuel Emegha had both missed.
Liverpool will face AFC Bournemouth in the quarter-finals.