An eighth-minute Daniel Wass own goal and Lucas Vazquez’s late strike earned Real boss Santiago Solari his sixth win from seven games since he took charge of the team in October.
Gareth Bale had a shot brilliantly saved by Neto, and Karim Benzema volleyed wide early in the match.
Valencia’s best chance fell to Santi Mina who fired over from 10 yards out.
The Spanish forward should have added to his six goals this season, but he snatched at the shot after an excellent first touch to control Daniel Parejo’s lofted ball. Ex-Arsenal defender Gabriel Paulista also went close for the visitors but he volleyed over at the far post from three yards out.
Defeat for Valencia leaves them 13th in the La Liga table, while Real are fifth and level on 23 points with fourth-placed Alaves. But Alaves, along with the three frontrunners – Atletico Madrid, Barcelona and Sevilla – play on Sunday.
Solari’s side gained an early advantage against Valencia on Saturday when Wass inadvertently headed in from close range from Dani Carvajal’s drilled cross.
Prior to the goal Benzema had gone close with a hooked volley before Neto produced an excellent stop to block Bale’s fierce effort. The Welshman was taken off in the second half – he has now gone 10 league games without a goal, his longest barren spell since joining Real in 2013.
Valencia had two great chances to equalise through Santi and Gabriel, before midfielder Vazquez slotted in his first league goal of the season from Benzema’s cross to seal the victory.