Title holders Barcelona were dumped out of the Copa del Rey and saw another trophy slip away as Xavi’s team lost 3-2 after extra time at Athletic Bilbao.
Athletic dominated the game and took the lead through Iker Muniain.
Ferran Torres netted this first goal for Barca to make it 1-1.
In the 86th minute, Inigo Martinez put Athletic back in the lead, but Pedri equalized in stoppage time.
Man-of-the-match Muniain scored the winner with a penalty in extra time, after VAR spotted a handball from Jordi Alba inside the area.
Athletic join Real Madrid, Real Sociedad, Valencia, Real Betis, Rayo Vallecano, Mallorca and Cadiz in the quarter-finals.
The draw will take place on Friday.