The quarter and semi-final draw was made on Friday morning at the House of European Football in Nyon, Switzerland.
In the other quarter-final ties, Premier League leaders Manchester City face Spanish champions Atletico Madrid and German giants Bayern Munich take on Villarreal.
The two-leg quarter-finals take place on 5-6 April and 12-13 April.
The first legs of the semi-finals will be on 26-27 April, and the second legs on 3-4 May.
Paris’ Stade de France will host the Champions League final on May 28 after it was moved from St Petersburg following Russia’s invasion of Ukraine.
Champions League draw
Chelsea (ENG) v Real Madrid (ESP)
Manchester City (ENG) v Atletico Madrid (ESP)
Villarreal (ESP) v Bayern Munich (GER)
Benfica (POR) v Liverpool (ENG)
Man City or Atletico Madrid v Chelsea or Real Madrid
Benfica or Liverpool v Villarreal or Bayern Munich
Chelsea are bidding to become only the second team after Real Madrid to retain the Champions League trophy and dispatched Lille in the round of 16.
But standing in Thomas Tuchel’s way is European giants Madrid and former Blues boss Carlo Ancelotti, who was in charge of the Stamford Bridge club between 2009 and 2011.
Real Madrid, the most successful team in Champions League history, are currently ten points clear at the top of La Liga and stunned Paris Saint-Germain in the last-16 round.
Liverpool beat Serie A side Inter Milan earlier in the month and have been rewarded with a draw against Portuguese outfit Benfica, arguably the weakest team left in the competition.
Jurgen Klopp’s side reached successive Champions League finals in 2018 and 2019, lifting the trophy in their most recent appearance.
Man City are yet to win the competition despite being the dominant force in England over the past decade – losing 1-0 to Chelsea in last season’s final – and meet Atletico Madrid after thrashing Sporting Lisbon in the previous round.
Spanish champions Atletico knocked Manchester United out at Old Trafford as they look to reach a third Champions League final under Diego Simeone.
Elsewhere, prolific winners Bayern Munich face underdogs Villarreal following their emphatic 8-2 aggregate win over RB Salzburg.
Bayern, who look on course to win a tenth successive Bundesliga title, are one of the favourites to win the Champions League but meet a Villarreal side who stunned Juventus in Turin this week.
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