
The match is a replay of the dramatic meeting between the two teams at a similar stage last season. Liverpool went 2-0 up through Andy Robertson and Mohamed Salah, only to be pegged back by a Marcos Llorente double.
Virgil van Dijk was the hero, scoring to make it 3-2 in the second minute of added time to send Anfield wild. Those are scenes the fans will be hoping are replicated again this time.
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There's been some changes in Liverpool since that game with Andoni Iraola replacing Arne Slot in the dugout. The Reds are also adapting to life without Salah.
In the build-up to the game, Liverpool have some players on the treatment table. Here's a look at the latest injury news from Anfield ahead of the visit of Diego Simeone's side.
The defender is yet to play this season due to a muscle injury, but is closing in on a return soon.
What Iraola has said: "The closest one is Joe," he said last week. "Joe will probably start training with us next week and it has gone normally, the recovery, from a muscle injury, more or less we were expecting the time on this. I hope we can have him before the break, let's say."
Potential return date: vs Fulham (H) (Sat 12 September)
The forward has missed every game so far this season due to a lower back injury.
Andoni Iraola has confirmed that the plan is for Chiesa to return to training during the international break.
Potential return date: vs Man City (H) (11 October)
What Iraola has said: "I think the next one probably should be Giovanni Leoni. I think the plan is also to start training during the break, with the group."
Potential return date: Late October
Injury: Achilles
Iraola has confirmed that the forward is not yet ready to return to training with the main group.
Potential return date: Unknown
Like Ekitike, Iraola has confirmed that he will will have to wait a bit longer to train with the main group.
Potential return date: Unknown