Bruno Soriano's brilliant free-kick was enough to earn Villarreal a fourth straight Primera Division win and inflict a first league defeat on Gary Neville as Valencia boss.
The Villarreal captain had already served notice of his ability from set-pieces when he found the top corner after 63 minutes with a curling left-footed strike which left Domenech Jaume with no chance.
The 1-0 victory at El Madrigal moved the Yellow Submarine up to fourth in the table, with Neville's men in 10th spot after picking up only two points from his opening three La Liga games in charge.
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Villarreal dominated the first half of this New Year's Eve clash but struggled to break down Valencia's well-organized defense.
Jonathan dos Santos had a shot saved low down by Jaume and Roberto Soldado fired wide from long range as Villarreal threatened in the opening minutes.
The hosts continued to do all the running and went close again when Bruno's left-footed free-kick flashed just past the right-hand post.
Villarreal picked up where they left off after the break as Denis Suarez jinked his way past two defenders before shooting inches wide.
But they were soon forced onto the back foot as Valencia enjoyed their best spell of the match. Andre Gomes saw two efforts blocked before Daniel Parejo had a shot well saved and Paco Alcacer blazed a golden opportunity over the bar.
Villarreal held off Valencia's charge and then broke the deadlock, Bruno stepping up to curl home a 25-yard free-kick after Aderlan Santos had gone through the back of Soldado.
Valencia responded positively and went close to equalizing when Alcacer volleyed Alvaro Negredo's knock-down just over.
But that was to be Los Che's last chance as Villarreal kept Neville waiting for the first league win of his managerial career.