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Cesc Fabregas tried his luck with a long shot in the sixth minute, but it was inadvertently blocked by Neymar, who was flagged for offside.
Cristiano Ronaldo had the first chance of the match for the visitors, but he smashed his effort from outside the box both high and wide.
Barcelona broke the deadlock two minutes later, as Neymar bursts into the box before sending a low effort in off Daniel Carvajal.
Lionel Messi almost made it two shortly after, but his curling effort swung just wide of the post, while the Argentinian also looked to score from a free kick just before half time, but Pepe made the block for Real.