
The victory put Los Meringues in second place of the league table with 57 points, two adrift of leaders Barcelona, who take on Villarreal on Sunday.
Dutch striker Ruud van Nistelrooy put the hosts in front in the 14th minute with a superb volley from the edge of the area after being set-up by Miguel Torres' inch-perfect cross.
Spanish international Fernando Morientes leveled the score seven minutes into the second-half after he was picked out unmarked inside the area before side-footing Joaquin's cross into the bottom corner of the net.
The introduction of former England skipper David Beckham, who is set to join MLS Soccer side LA Galaxy at the end of the season, was decisive in helping Real restore their lead.
He swung in a free-kick which was headed by Real defender Sergio Ramos past Valencia keeper Santiago Canizares in the 73rd minute.
Elsewhere, Real Sociedad registered a crucial 2-0 victory over nine-man Atletico Madrid in their bid to avoid relegation.
Darko Kovacevic grabbed the opener after seven minutes before Atletico suffered a huge blow after Peter Luccin and Fabiano Eller were sent-off in the 71st and 82nd minutes respectively.
Sociedad capitalized on their numerical advantage succeeded in adding the second six minutes from time through Savio.
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