Ex-Bournemouth striker Arnaut Danjuma was on target for the home side to stun the German champions.
Villarreal were superb from the outset and led inside 10 minutes when Danjuma stabbed in from close range.
Francis Coquelin had a goal ruled out while Gerard Moreno hit the post as the Spanish side pushed for a second.
Bayern were well below par and did not manage a shot on target until the second half.
Robert Lewandowski, who has scored 51 goals for club and country this season, was kept quiet by a well-organised Villarreal defence as the hosts followed up their impressive win against Juventus in the previous round with another big result.
But as poor as Bayern were they will feel they can turn things round against the Spanish side in the return leg on Tuesday, 12 April.
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