This was the chance for Real Madrid to go four points clear of Barcelona in the first of two games in hand but they fell behind early when Simone Zaza scored after just five minutes.
And what a goal it was. Valencia goalkeeper Diego Alves launched his team first real attack down the right and Munir El Haddadi crossed for Zaza, who made light of having his back to goal and Raphael Varane for close company by spinning 180 degrees and firing into Keylor Navas’ top right-hand corner in one movement.
Four minutes later and it was 2-0. Once again the lightning break came down the right. This time Munir fed Zaza, who played in Nani who fed Fabian Orellana who buried the chance. Two winter signings for Valencia and both had scored.
Real Madrid tried to fight fire with fire and Cristiano Ronaldo had a shot saved by Alves. James Rodriguez then tried to convert Ronaldo’s cross at the far post but Munir had sprinted back to save on the line.
Real Madrid kept chasing the game and the Valencia threat was reduced when Nani had to hobble off and Guilherme Siqueira came on to make it double full backs for the home side down the left.
It was Nani’s Portugal team-mate who was next to make his mark on the game. Marcelo crossed with the outside of his left-foot and Ronaldo rose above the Valencia defence and hung in the air long enough to guide the centre past Alves for 2-1.
No one has scored more headed goals than Ronaldo in Europe’s top league over the last 10 seasons. He has 51, two more than Swansea’s Fernando Llorente.
Real Madrid started the second half as they finished the first but they couldn’t make the pressure pay and Valencia could have had two penalties on the break.
First Zaza raced away for what could have been his second of the game but Dani Carvajal barged him off the ball just as he was about to shoot past Keylor Navas. Then Munir raced away and went down after Ramos stood on his ankle just inside the area.
Valencia had their own slice of luck when Eliaquim Mangala scythed down Karim Benzema and was only shown the yellow card. Zaza hobbled off with 18 minutes left and the sight of midfielder Mario Suarez replacing him sent out the message – we hold what we have. But could they?
Gareth Bale had appeared at the hour mark and Valencia were shaking at the back every time Real Madrid poured forward. But with the excellent Ezequiel Garay blocking Bale’s late header in the six-yard box, Valencia held on for a famous win.
Real Madrid full back Marcelo admitted: ‘There is no excuse. We started the game very badly and it’s our fault. We are still top but we have to learn from this mistake. We can’t start games this way.’
Madrid remain a point clear of Barcelona but now have just one game in hand and Valencia have done the rest a favour by proving Zinedine Zidane’s team are not invincible.