Barcelona, the defending champion, was expelled from the King's Cup, Thursday, after losing 3-2 to its host Athletic Bilbao after extra time in the final price round.
Bilbao advanced with a superb shot from Iker Muniain against Marc-Andre ter Stegen.
Newcomer Ferran Torres equalized for the away team with a shot from the edge of the penalty area, scoring his first goal with the Catalan team.
Iñago Martinez restored Bilbao's lead 4 minutes before the end, but Barcelona forced their hosts to go into extra time after Pedri equalized in stoppage time.
Munayen decided Bilbao's victory with a penalty awarded by the referee after consulting the VAR for a handball against Jordi Alba.