They are joined by fellow title-winners Bayern Munich, Real Madrid, Juventus, Paris Saint-Germain, Zenit St Petersburg and Porto, along with the winners of last season’s Europa League, Sevilla.
Liverpool can, therefore, not be drawn against any of those sides in the group stage, with one from each of Pots 2, 3 and 4 to be their opponents for the rest of the year.
Tuesday night saw Benfica lose their third qualifying round clash with PAOK, which relinquished the final spot in Pot 2 to Ajax.
With the Reds unable to meet fellow English sides in the group stage, that leaves just five sides from Pot 2 that they can be drawn against.
These five present a mix of interesting clashes for Liverpool, including the side who knocked them out of last season’s tournament, Atletico, and the one they famously humiliated in the semi-finals in 2019, Barca.
Dortmund would be a romantic draw for Jurgen Klopp, while Ajax would be a rare opponent for the Reds, with the two sides having only met twice before in competitive games, both being in 1966.
Shakhtar would be the most difficult in terms of travel, but would also ensure a first-time meeting.
RB Leipzig, Inter Milan, Lazio and Atalanta are already confirmed for Pot 3, and are most likely to be joined by Dynamo Kyiv, Salzburg, Olympiakos and Krasnodar.
Pot 4 includes Borussia Monchengladbach, Rennes and Istanbul Basaksehir, with the likes of Lokomotiv Moscow, Marseille and Club Brugge qualified and potentially included too.
The draw for the Champions League group stage will be held at 5pm (BST) on Thursday, October 1, with the final pots to be determined by September 30, when the playoffs are concluded.
Champions League Group Stage Pots (So Far)
Pot 1: Bayern, Sevilla, Real Madrid, LIVERPOOL, Juventus, PSG, Zenit, Porto
Pot 3: RB Leipzig, Inter Milan, Lazio, Atalanta
Pot 4: Borussia Monchengladbach, Istanbul Basaksehir, Rennes
Pot 3 or 4: Lokomotiv Moscow, Marseille, Club Brugge
Yet to qualify:
Slavia Prague or Midtjylland/Young Boys
Maccabi Tel Aviv/Dynamo Brest or Salzburg
Olympiakos or Omonia/Red Star
Qarabag/Molde or Ferencvaros/Dinamo Zagreb
Krasnodar or PAOK
Gent or Dynamo Kyiv