Pep Guardiola's side comfortably overcame Los Che and will look to the final in May as it looks to rectify last season's defeat against Real Madrid.
With the cushion of Carles Puyol's away goal in the 1-1 draw at the Mestalla, the Catalans were in imperious form as Cesc Fabregas' first-half strike and a Xavi thunderbolt were enough to help the Catalans reach their 36th Copa del Rey final.
Barcelona struggled to settle in the early exchanges and Valencia was presented with a good chance to take the lead. Jeremy Mathieu's curling ball found Sofiane Feghouli's dart forward but the Frenchman's rasping drive was off target.
Despite their confident start, Los Che found themselves behind in the 16th minute when Lionel Messi's lofted pass caught Diego Alves in two minds. His indecisiveness allowed Fabregas to clip the bouncing ball past the Valencia 'keeper from an acute angle.
The Catalans could have doubled their lead when Messi intercepted Adil Rami's forward pass giving the Argentine a sight of goal only for Diego Alves to parry his shot away. A stationary Valencia defense watched in desperation as Isaac Cuenca was first to react to the loose ball but the youngster skewed his effort wide.
But for Diego Alves, Valencia would have found itself two goals down as it play continued to be littered with mistakes, but the Brazilian stopper thwarted Fabregas twice with smart saves.
In a similar fashion to the first half, Valencia created a superb opening when Jordi Alba was played in. The Spaniard's premier touch took him away from the hounding Carles Puyol and with his second he lashed the ball toward goal only to be denied by Jose Pinto.
Barcelona responded when Messi demonstrated his supreme talent by evading four Valencia defenders with one sultry touch before bringing out a first-rate reactionary save from Diego Alves with an unsightly toe-poke.
The two players traded blows once more but Messi was once denied by the Brazilian stopper leaving the striker with a prolonged look of disbelief on his face.
Puyol became Barcelona's saviour when he cleared ahead of the waiting Jordi Alba with an acrobatic clearance. And Pinto was forced to tip Jonas' thunderous drive over the bar soon after as Valencia began to attack relentlessly.
Valencia's task progressed from improbable to impossible when Feghouli was shown his second yellow card, leaving Los Che a man light needing a goal in the remaining 13 minutes to keep alive their Copa del Rey hopes.
Soon after Aduriz had wasted a chance to level, Xavi destroyed any glimmer of hope with an emphatic finish following a swift Barca break.
Diego Alves continued to deny Barcelona with a string of saves in the final moments, significantly a wonderful diving save from Messi's free kick.
Guardiola's side, looking for its 26th Copa del Rey victory, will be looking to rectify last seasons defeat against Real Madrid when it meets Athletic Bilbao, which has lifted the trophy 23 times, in May.