The game followed the pattern of the first leg at the Nou Camp with Valencia successfully packing the midfield and looking to hit the visitors on the break.
Gabriel Milito's header from a corner was pushed against the crossbar early on as Barca pressed forward, but the opener came at the other end when midfielder Baraja scored with a rasping drive from outside the area in the 18th minute.
The 24-times winners struggled to pass their way through Valencia's massed ranks and were hit in a swift counter-attack a minute before the break when David Villa fed Mata to finish inside the near post.
Barcelona's Thierry Henry and Valencia's Carlos Marchena (L) fight for the ball during their Spanish King's Cup semi-final second leg soccer match at the Mestalla Stadium in Valencia March 20, 2008.
Frank Rijkaard turned to Henry after the restart and the France striker headed in off the post from Silvinho's cross in the 72nd minute, but almost immediately David Silva escaped on the right and crossed for Mata to volley past Victor Valdes. Barca threw bodies forward and Cameroon striker Eto'o broke into the area to curl the ball inside the far post with 10 minutes remaining but it was not enough to stop Barca going out in the semis for the second season running.
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