The hosts went into the game knowing that they had to beat Barca to advance the Copa del Rey final, but ultimately fell to defeat at the Mestalla.
Both sides threatened early on in an entertaining opening to the game, with Francis Coquelin and Lionel Messi forcing saves from Jasper Cillessen and Jaume Domenech respectively.
Valencia thought they had taken the lead with 14 minutes gone, only for Rodrigo’s header from a Jose Gaya cross to crash back off the upright.
Barca dominated possession for the rest of the half but struggled to create any gilt-edged chances, with Messi seeing a curling effort from range drift just wide, before Rodrigo responded by stinging Cillessen’s palms with a powerful drive.
As the half drew to a close both sides had chances to open the scoring.
First, Luis Suarez could only shoot straight at Jaume after receiving the ball in the box, before Geoffrey Kondogbia fired into the side-netting after gathering a cross form the right.
That meant that the two sides went into the break level, but it didn’t stay like that for long.
- Coutinho’s instant impact -
Philippe Coutinho was summoned for the second half and the Brazilian made an instant impact, meeting Suarez’s cross from the left at the far post to break the deadlock with a sliding finish.
That goal left Valencia needing three to progress, but they stuck to their task, aided by the introduction of livewire Gonçalo Guedes on his return from injury.
Suarez went close to continuing his fine form in front of goal as he curled an effort just wide of the far post, before Carlos Soler did likewise at the other end.
Messi thought he had sealed the game just after the hour mark, only for his effort to be kept out by Jaume after meeting a cutback from the right.
Valencia weren’t without their chances though, with Guedes flicking an effort onto the roof of the net and Cillessen somehow denying Gaya from six yards with a stunning point-blank save.
However, as time passed, ‘Los Che’ threw more and more men forward, leaving themselves open at the back, with Barca taking full advantage.
As the game entered it's final knockings, former Arsenal man Gabriel Paulista surrendered possession cheaply and Suarez was in quick as a flash, the Uruguayan squaring for Ivan Rakitic who duly stroked an effort across Jaume and into the far corner to secure the victory.
The defeat is Valencia sixth in a row in all competitions, whilst Barca advance to the final of the competition they won last year and will face Sevilla.