Barcelona left it late on Saturday as Robert Lewandowski scored an injury-time winner to give the visitors all three points at the Mestalla.
It was a tightly contested game that saw bouts of brawls from both sides.
Both teams had a goal apiece ruled out as they sought to find the lead in what was an evenly matched tie.
Lewandowski would, however, sretch length to connect to a Raphinha’s pass and get the ball past the Valencia into the net in stoppage time to quiet the crowd at the Mestalla.
The win sends Barca to top of the league, leveled on points with Real who play on Sunday against Girona.
