Villarreal welcomed Espanyol to the Camp El Madrigal on Thursday looking to make it 14 points from their first six games of the season.
The home side were ahead inside one minute when Jeremy Perbet converted from close range, with that strike all that separated the two sides at the interval.
Espanyol pressed for an equaliser in the second period, but they fell 2-0 behind after 67 minutes when Jonathan Pereira converted from close range.
Sergio Garcia had one back for the away side late on, but it was a case of too little too late as their unbeaten run came to an end.
Read how it all unfolded in Sports Mole's minute-by-minute live commentary of the action below.
VILLARREAL: Asenjo; Musacchio, Mario, Costa, Iniguez; Cani, Bruno, Perez, Pina; Perbet, Giovani
ESPANYOL: Casilla; Sidnei, Moreno, Mattioni, Rodriguez; Clerc, Abraham, Lanzarote, Alex; Garcia, Bifouma