The record German champions won through to this stage of the competition after thrashing Red Bull Salzburg 8-2 on aggregate, having previously topped Group E ahead of Benfica, Barcelona and Dynamo Kyiv.
Robert Lewandowski is the 12-goal top scorer in this season's competition, scored at a rate of one every 57 minutes he has played.
Bayern and Villarreal have only played each other twice in this competition, in the group stages of the 2011/12 campaign. The Germans came out on top on both occasions, winning 2-0 at La Ceramica and 3-1 at the Allianz Arena.
Bayern have been crowned European champions six times, most recently in 2020 when they won an unprecedented sextuple under current Germany manager Hansi Flick.
The draw in full
Chelsea vs. Real Madrid
Manchester City vs. Atletico Madrid
Villarreal vs. Bayern Munich
Benfica vs. Liverpool