Title holders Chelsea are up against their former coach Carlo Ancelotti as they were on Friday drawn to play record winners Real Madrid in the Champions League quarter-finals.
Atletico Madrid meanwhile return to Manchester to face last year's finalists City, after eliminating Man United in the last 16.
The winners of those April 5/6 and 12/13 ties will then meet in the semi-finals April 26/27 and May 3/4 which could lead to a repeat of the 2021 final or a Madrid derby.
Six-time winners Liverpool and Bayern Munich were drawn to play away first, at Benfica and Europa League champions Villarreal, respectively.
The two winners make up the other semi-final en route to the May 28 final at the Stade de France, in a move of location as St Petersburg was stripped of the game after Russia's invasion of Ukraine.
Chelsea have never lost against 13-time champs Real in Europe, winning three matches and drawing the other two, and beating them 3-1 on aggregate in last year's semi-finals.
Ancelotti coached the Blues 2009-2011 and goalkeeper Thibaut Courtois and often injured Eden Hazard are two former Chelsea players now within Real's ranks.
Villarreal, Atletico Madrid
Bayern board member sport Hasan Salihamidzic said they would not underestimate Villarreal who advanced with an impressive 3-0 win at Juventus in mid-week.
"I played at Juventus and know how difficult it is to get a 3-0 victory there. We are up against a good team and should not underestimate this challenge," he said.
But, coming off an 8-2 aggregate win over Salzburg, he added: "We are Bayern and we will travel there with a lot of confidence."
A Bayern v Liverpool semi could be on the cards but the Reds can not afford to underestimate Benfica who eliminated them in their last meeting in 2005-06.
"It was a difficult draw, challenging for us," Benfica director Luisao told uefa.com.
"In 2006 we faced Liverpool and they were the holders, and we went through. Liverpool are a very strong team. They have high-level players, also in defence, but where they are strongest is really the attack."
Atletico captain Koke meanwhile said that Pep Guardiola's City are a big task but was confident that his coach Diego Simeone "will come up with a strong plan to get us through the tie.
"They’re one of the favourites. Last season, they came very close to winning the Champions League. They have a great coach and players, and play great football, but we like that sort of challenge," Koke said.