Leo Baptistao scored past his parent club to put Villarreal 1-0 up at half time against Atletico Madrid at the Estadio El Madrigal.
Villarreal went ahead after 14 minutes after Baptistao exchanged passes with Roberto Soldado before the 23-year-old slotted the ball past Jan Oblak in the Atletico goal.
The Brazilian then repaid the favour to Roberto Soldado moments later, with the Spaniard managing to get his strike on goal but Oblak was equal to it and diverted it away.
Samu Castillejo came close to making it two after stooping low to meet a cross from the right but the 20-year-old could not direct his diving header inside the post.
Atleti top scorer Antoine Griezmann had a chance on the brink of half time but the Frenchman could not beat Alphonse Areola in goal one-on-one.
