Luis Suarez celebrate his goal with his Barcelona teammate as they advance to the final of Copa del Rey
Barcelona won 6-2 on aggregate and will play Athletic Bilbao in the final on May 30.
Neymar opened the scoring in the third minute by tapping home a perfectly lofted entry pass from Lionel Messi.
Villarreal equalised on the night through Jonathan Dos Santos six minutes before half-time. Jaume Costa's cross from the left sailed over defenders and fell to Dos Santos at the far post.
But play opened up after Tomas Pina, whose earlier tackle saw Sergio Busquets stretchered off, was dismissed on 65 minutes for a lunging tackle that caught Neymar's foot.
In the 73rd minute, Luis Suarez rounded Villarreal keeper Sergio Asenjo to score his sixth goal in four games in all competitions.
Neymar was again left alone in the box to head home a lofted pass from Javier Mascherano to clinch the win two minutes from time.
Aritz Aduriz and Xabier Etxeitia each scored in the first half to carry Athletic Bilbao to a 2-0 win at Espanyol.
With the scores 1-1 after the first leg, the visitors took the lead after 13 minutes as the home defence failed to clear Oscar de Marcos' cross and Aduriz picked the ball up and slotted past a diving Pau into the bottom corner for his 15th goal this season.
Bilbao went 2-0 up just before the break as Etxeita headed home from Andoni Iraola's corner to complete a 3-1 aggregate victory and set up a final clash with Luis Enrique's men.
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