Cristiano Ronaldo marked his 700th club appearance with a powerful header on the stroke of half-time but Real could not force an equaliser despite late pressure.
The result means Zinedine Zidane's side remain one point clear of second-place Barcelona having played a game less.
Meanwhile, Valencia's second straight win eases their relegation worries, moving them 10 points clear of the drop zone.
Gareth Bale, who made a goalscoring return in the 2-0 win over Espanyol on Saturday, started from the bench as Zidane made seven changes
.
But the league leaders were twice caught out on the counter attack as Valencia stormed into an early lead.
Zaza made it two goals in two games with a stunning strike on the turn from Munir El Haddadi's low cross and Orellana capped a flowing move to double Valencia's advantage five minutes later.
An injury to Nani shortly before half-time interrupted their rhythm and Real earned a foothold in the match through Ronaldo.
Marcelo delivered from the left and the Portugal captain rose between
two defenders to plant a trademark header past Diego Alves.
He almost grabbed a quick-fire second in first-half added time when his effort from distance flew narrowly wide via a deflection off Eliaquim Mangala.
The Manchester City loanee, who was otherwise excellent, was fortunate to avoid conceding a penalty shortly after half-time following a collision with the Real goalscorer.
He almost grabbed a quick-fire second in first-half added time when his effort from distance flew narrowly wide via a deflection off Eliaquim Mangala.
The Manchester City loanee, who was otherwise excellent, was fortunate to avoid conceding a penalty shortly after half-time following a collision with the Real goalscorer.
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