Madrid, which clinched the title on Sunday, improved its record against its arch rival to 68-30-58 and only one loss their last seven meetings. It climbed to 81 points atop the table, 10 better than Villarreal and 17 ahead of third-placed Barcelona.
Jose Maria "Guti" Gutierrez lost possession trying to get by Rafael Marquez in the 13th minute and Raul pounced on the loose ball to shoot past goalkeeper Victor Valdes.
Barcelona's defense was to blame when Robben ran clear through in the 21st to meet Guti's free kick. Gonzalo Higuain, who scored the clinching goal in Sunday's 2-1 victory against Osasuna, added another in the 63rd - less than a minute after replacing Robben.
"When you get the chance to score lots of goals, you have to take it. The first two did a lot of harm," Madrid coach Bernd Schuster said.
Substitute Van Nistelrooy converted a penalty in the 78th while Thierry Henry tallied a consolation goal for Barcelona with three minutes remaining.
In Wednesday's other 36th-round of games, it was: Racing Santander 0, Sevilla 3; Valencia 1, Zaragoza 0; Getafe 4, Almeria 2; Recreativo Huleva 0, Villarreal 2; Real Betis 1, Valladolid 1; Mallorca 2, Osasuna 1; Deportivo La Coruna 1, Levante 0; and Murcia 1, Athletic Bilbao 2.
Barcelona's defeat likely will add to speculation that Frank Rijkaard will not remain as manager of the Catalan club following a second straight season with out a trophy.
Adhering to tradition, Barcelona honored the champion as Real Madrid entered the Santiago Bernabeu field - the first time in 20 years the Catalans have formed the passage of honor for their longtime rivals.
"We tied down there offensive play, neutralizing Messi for example," Schuster said. "We wanted to round things off in front of our fans after winning the league."
Madrid started enthusiastically and limited Barcelona forward Lionel Messi to a first touch in the 10th before a deserved opener.
Bojan Krkic skied Barcelona's first chance over goal in the 24th and Henry curled wide two minutes later.
But Madrid was unrelenting and Valdes got his hands up to save Guti's rising shot from the left in 34th. Barcelona was sloppy at the other end with Henry unable find the open Giovani Dos Santos streaking in alone down the right.
"It was clear that we didn't play a good game. You could see the difference between a team that has won, that has a trophy and one that has suffered," Rijkaard said. "Everything went in favor of Madrid."
Robben volleyed over before Sergio Ramos' hard centering pass got by the open Raul at the far post in the 43rd.
Substitute Silvynho saved a sure goal in the 56th by poking away from Marcelo as the Brazilian defender ran clear onto Guti's centering pass.
Xavi cleared Ramos' shot off the line in the 60th before Valdes pawed Marcelo's hard rising shot out in the 67th.
Van Nistelrooy, making his first appearance since ankle surgery on March 24, scored a minute after replacing Raul and was denied by Valdes two minutes later.
Madrid goalkeeper Iker Casillas denied Messi in the 82nd and 86th before the Argentina winger put Henry through to score.
Xavi was ejected two minutes into injury time with a second yellow car after exchanging words with the referee.
At Santander, Federico Fazio scored two goals as Sevilla overtook Racing and temporarily moved into a tie with Atletico Madrid for fourth at 58 points. Atletico plays Thursday against Espanyol.
Racing dropped to sixth with 56 points with the top four teams qualifying for European Cup play.
David Silva, who was ejected with four minutes remaining, scored in the 20th minute as Valencia beat Zaagoza 1-0 to move closer to salvation with four of its relegation opponents failing to win.
Manuel del Moral scored two goals as Getafe rallied from a two-goal deficit for a 4-2 win against Almeria that left it tied with Valencia on 45 points.
Fifteenth-ranked Valladolid, Zaragoza, Recreativo and No. 18 Osasuna were separated by three points in the relegation race with only two games remaining for each.
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