A stunning free-kick from Bruno allowed Villarreal to see off a stubborn Valencia with a 1-0 win at El Madrigal on Thursday.
Marcelino's men controlled the majority of the opening hour but it took a special strike from the captain to break the deadlock in the 64th minute.
Valencia offered a disciplined display but rarely looked likely to threaten an equaliser, meaning Gary Neville's wait for a first Liga win as head coach goes on, while Villarreal are now back to within three points of third-placed Real Madrid.
Bruno whistled a free-kick narrowly wide of Jaume Domenech's right-hand post as the home side started proceedings in the ascendancy.
The lively Jonathan dos Santos, who had earlier tested Domenech low to his right, rasped a shot from distance narrowly over as Villarreal continued to press throughout the first half without success.
Marcelino's side picked up where they left off after the break, Denis Suarez fizzing a low shot just past the far post after cutting in from the left before Cedric Bakambu could only shoot straight at Domenech after a fine link-up with Roberto Soldado.
Andre Gomes' fine run brought the first save out of Alphonse Areola, before Dani Parejo forced the goalkeeper into a one-handed stop from distance as Valencia began to offer some attacking intent just prior to the hour mark.
But Villarreal took the lead shortly afterwards as Bruno, from an almost identical position to his first-half effort, curled a stunning free-kick into the top-left corner from 20 yards.
Valencia pushed forward in the closing stages, but they rarely managed to threaten Areola's goal as Villarreal saw out a well-deserved victory.