Arsenal have been drawn against Borussia Dortmund in the 2014-15 Champions League draw in Monaco, while Premier League champions Manchester City will face Bayern Munich.
The Gunners overcame Besiktas in a nervy play-off clash thanks to Alexis Sanchez's first goal for the club to reach competition proper for the 17th consecutive season, and will now face Dortmund, Galatasaray and Anderlecht in Group D.
Liverpool mark their return to the competition for the first time since 2009 with clashes against Real Madrid, Basel and Ludogorets in Group B. The Anfield outfit have never tasted defeat to the Spanish giants after three meetings.
Manchester City reached the knockout stages of the competition for the first time in their history last season, only to be eliminated by Barcelona in the round of 16.
They have been handed a tough draw with Pep Guardiola's Bundesliga champions and CSKA Moscow in Group E.
Jose Mourinho, who has won the trophy with both Porto and Inter, guided Chelsea to the semi-finals last season before losing out runners-up Atletico Madrid.
The London side has been drawn against Schalke – who they have never conceded against – and Sporting in Group G.
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