Goals from Daniel Pajero, Pablo Piatti and Paco Alcacer secured a shock 3-2 win over Barcelona at the Camp Nou.
Alexis Sanchez opened the scoring in the seventh minute with a neat finish from close range, following a cross from Lionel Messi.
Dani Alvez nearly doubled the hosts advantage in the 22nd minute, the Brazilian sliced his effort wide of target after being picked out by Xavi Hernandez.
Sanchez came close to increasing the lead just a minute later as the Chilean got on the end of Pedro's cross only for Alvez to make a brilliant save from close range.
Lionel Messi was next to have a effort on goal in the 25th minute, but Deigo Alvez got down well to deny the Argentinian's shot from the edge of the area.
Valencia's first meaningful opening came in the 39th minute as Jeremy Mathieu pounced on some poor goalkeeping by Victor Valdes but the defender could only poke his effort wide.
Daniel Pajero eqaulised for Valencia in the 44th minute with a finish from close range, after some good work by Sofiane Feghouli.
Pablo Piatti put Valencia ahead in the 48th minute, the midfielder rose the highest to head over Valdes.
Lionel Messi equalised for the home side in the 53rd minute from the penalty spot, after Alberto Costa was adjudged to have handle the ball in the box.
Six minutes later and Valencia regained the lead through Paco Alcacer, the striker whipped in a wonderful effort, following a cross form Feghouli.
Dani Alvez came close with a long range effort in the 83rd minute but the fullback's shot whistled just wide of the post.
Messi squandered a great chance deep into stoppage time, the Argentine danced his way into the box before rolling his effort just wide of the post.