Both teams rose to the occasion in a breathless, high tempo affair, and it was the home side who did most of the early pressing. Jonathan dos Santos went close with a shot saved by Domenech, and moments later it was Soldado's turn to set his sights on goal as he flashed a half-volley wide. Bruno also came close with a free kick that whistled past the post.
With Valencia setting up in a 3-5-2 formation, it was obvious that the gameplan was to stifle and frustrate the hosts and they stuck to their task in the first half. The Yellows played with a verve and freedom that was a joy to watch, but they couldn't find a way past some stubborn Valencia defending and it remained goalless at the interval.
After the break, Villarreal continued to dominate proceedings and Denis Suárez went close after robbing Barragán of the ball but his low shot went just wide. Suarez was a constant menace down the left-flank, and on this kind of form the Yellow Submarine will be hard-pressed to keep hold of the young midfielder.
Valencia had posed little attacking threat up till this point but enjoyed a brief spell on the hour mark with Dani Parejo striking a warning shot from distance that brought a one-handed save from Areola, and striker Paco Alcácer blasting an effort over the bar from a cutback.
However, in the 64th minute it was Villarreal who opened the scoring. Soldado was fouled on the edge of the box and from the resulting free-kick captain Bruno broke the deadlock with a sublime shot into the top left-hand corner.
Valencia huffed and puffed but couldn't find an equalizer, despite making three attacking changes.
This win lifts the Yellow Submarine above rivals Celta Vigo into 4th spot and three points behind Real Madrid, while Valencia's new boss Gary Neville is left searching for his first league victory.
Villarreal (0) 1
Areola; Mario, Musacchio, Ruíz, Adrián Marín; J. dos Santos (Nahuel 67'), Trigueros (Pina 74'), Bruno, Denis Suárez; Soldado, Bakambu (Baptistão 80')
Subs not used: Barbosa (GK), Rukavina, Castillejo, Samu
Goals: Bruno 64'
Bookings: Soldado 68'
Valencia (0) 0
Doménech; Barragán (Santi Mina 69'), Rúben Vezo, Abdennour, Santos, João Cancelo; André Gomes, Dani Parejo (Villalba 87'), Danilo (Piatti 74'); Negredo, Paco Alcácer
Subs not used: Ryan (GK), Orbán, Javi Fuego, R. de Paul
Bookings: André Gomes 16', Barragán 45', Villalba 90+2'
Manager: Gary Neville