Williams came off the bench near the hour mark on Wednesday, two days after Ghana's last match in Ivory Coast. He scored off the rebound of his own shot into the post in the 107th minute. His younger brother, Nico Williams, then sealed the victory in stoppage time, sending Athletic to the last four for the fifth straight season.

It was another tough blow for Barcelona, which was looking to make it to the Copa semifinals for the second straight season. The Catalan club earlier this year had already missed another chance to win a title when it lost 4-1 to Real Madrid in the Spanish Super Cup final in Saudi Arabia.

Barcelona had been eliminated by Athletic in extra time in the round of 16 of the Copa in 2022.

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Athletic finished runner-up in 2019-20 and 2020-21, and was eliminated in the semifinals the last two seasons — by Osasuna in 2023 and Valencia in 2022. The Basque Country club last won the competition in 1984.

Williams started on the bench after arriving in Spain the morning of the match between the two most successful clubs in the Copa — Barcelona has 31 titles and Athletic 23.

The 29-year-old forward entered the match in the 59th and didn't waste his chance in extra time, finding the net from close range after his initial attempt from inside the area struck the post.

“Not even in the best of my dreams I could have imagined this,” Williams said. “Everything turned out perfect. Yesterday I didn't imagine being here after a tough blow (with Ghana).”

The son of Ghanaian parents who moved to Spain before he was born, Williams had disappointing appearances as Ghana failed to make it past the group stage in the Africa Cup. He didn't score any goals as Ghana returned home after a loss and two draws.

It was an open match at San Mames Stadium, with both teams having significant scoring chances.

Teenager Lamine Yamal had a golden chance to score Barcelona's winner in regulation in a one-on-one situation in the 86th, but he missed the open net from inside the area after dribbling past Athletic goalkeeper Julen Agirrezabala.

“When you have a single-elimination game on the road it's difficult to win,” Barcelona coach Xavi Hernández said. “It's how it goes in the Copa.”

Athletic took the lead with a goal by Gorka Guruzeta a minute into the match.

The visitors rallied with Robert Lewandowski scoring in the 26th and Yamal in the 32nd after a nice run by the 16-year-old forward. Lewandowski's goal was a fortuitous one as the ball ricocheted off his leg while a defender tried to clear it from in front of the net.

Athletic evened the match with a header by Oihan Sancet in the 49th. Barcelona defender Alejandro Balde had to be replaced only 23 minutes into the match because of an apparent muscle injury.

Athletic, sitting fifth in the Spanish league, had won six straight games in all competitions before losing 1-0 at Valencia in the league on Saturday.

Barcelona, third in the Spanish league, had won six of its last seven matches across all tournaments.

Girona Eliminated 

Spanish league leader Girona lost 3-2 to Mallorca and missed its chance to reach the Copa semifinals for the first time.

The hosts were up 3-0 by the 35th minute thanks to goals by Cyle Larin, Abdón Prats and Antonio Raíllo. Girona scored with Cristhian Stuani in the 68th and Savinho in stoppage time.

Girona played a man down from the 67th after Raíllo was sent off with consecutive yellow cards for the foul that led to a penalty kick and for complaining to the referee.

On Tuesday, Real Sociedad defeated Celta Vigo 2-1 to reach the Copa semifinals for the first time since winning the competition four seasons ago.

On Thursday, Atletico Madrid — which eliminated defending champion Real Madrid in the round of 16 — hosts struggling Sevilla, which sits just outside the relegation zone in the Spanish league.