Barcelona's journey in this season's Copa del Rey ended on Wednesday night following a 4-2 defeat at Athletic Bilbao after extra time.
Girona also exited the tournament at the quarter-final stage on Wednesday by losing 3-2 at Sevilla.
That means that the top three teams in La Liga have all failed to make the semi-finals of Spain's top cup competition - Real Madrid lost to Atletico Madrid in the round of 16.
Bilbao took the lead against Barca after just 36 seconds when Gorka Guruzeta fired home from nine yards following some chaotic defending.
Robert Lewandowski equalized in the 26th minute when he charged down an attempted clearance by Yuri Berchiche and the ball deflected into the net.
A superb solo goal from Lamine Yamal then put the visitors in front before half-time.
But an Oihan Sancet header drew Bilbao level at 2-2 early in the second half.
Yamal missed a golden chance to win the game for Barca in the 85th minute before the game went to extra time.
Substitute Inaki Williams - just 48 hours after playing for Ghana at the Africa Cup of Nations - then made it 3-2 to Bilbao when he converted his own rebound after initially hitting the post.
Nico Williams then finished Barca off in added time at the end of extra time with a stylish strike from 17 yards using the outside of his right boot.
Highlights: Athletic Bilbao 4-2 Barcelona
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