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.
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