Real's triumph condemned Barca to three successive defeats for the first time since January 2003 and crushed the Catalan team's final realistic chance of winning silverware this season.
It capped off a miserable seven days for Gerardo Martino's Barca, who were last week knocked out of the Champions League by Atletico Madrid before losing at Grenada in La Liga on Sunday.
While Real's big-money recruit flourished, Barca's star signing floundered.
Neymar arrived at the Nou Camp amid much fanfare last June, but the Brazilian spurned a glorious opportunity to level the match in the final moments when he fired a close-range effort against the post.
The first goal of a tense contest at Valencia's Mestalla Stadium arrived on 11 minutes after a rapid Real counter attack.
Bale set Angel di Maria racing free and the Argentine composed himself before firing a low shot through goalkeeper Pinto and into the corner of the net.
Pinto's attempts to save the shot had Barca fans pining for Victor Valdes, the team's longstanding goalkeeper who is unavailable after tearing his anterior cruciate ligament last month.
Real had injury problems of their own with FIFA Ballon d'Or winner Cristiano Ronaldo missing through a hamstring injury, although his absence was barely felt as Los Blancos dominated the first half.
Barca struggled to match their vibrant opponents, with Lionel Messi cutting a particularly forlorn figure.
It looked as if Bale had doubled Real's lead midway through the second period, but the winger saw his close-range header chalked off. Moments later, Barca found an equalizer from the unlikeliest of sources.
Young defender Marc Bartra chose the perfect time to score a rare goal as he powered a firm header beyond Iker Casillas from Xavi's 68th-minute corner.
But Real, and Bale, were not to be denied.
With 85 minutes on the clock and extra-time looming large, Bale unleashed a punishing burst of pace to surge past Bartra near the halfway line.
Bale soared towards goal and, under pressure from the pursuing Bartra, coolly poked a shot under the advancing Pinto.
Barca should have leveled in the 90th minute, but Neymar could only find the post when presented with a clear sight of goal.
While Martino's men must now contemplate a somber end to the season, Real have it all to play for.
Ancelotti's team face Bayern Munich in the Champions League semifinals, while they also sit just three points behind city rivals Atletico at the top of the La Liga table.
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