Álex Berenguer scored in the 89th minute to give Athletic a 1-0 victory in the quarterfinal at San Mamés Stadium on Thursday, ending a three-match losing streak for the Basque Country team against Madrid.
Unai Emery's Villarreal lost 2-1 at Sporting Gijon after the second-division side came from behind while Osasuna were ousted by second-division Girona 1-0
Madrid needed two late goals to beat Alcoyano 3-1 while Barca had to come from behind to beat third-tier Linares Deportivo 2-1.
Real Madrid vs Alcoyano Live Streaming: Get full details on when and where to watch Copa Del Rey 2021-22 Live Streaming football Online.
Carlo Ancelotti's side, who saw their 11-game unbeaten run come to an end against Getafe on January 2, will eye revenge as they travel to face third-tier team Alcoyano.
Sociedad ended a three-decade title drought on Saturday when it beat fierce Basque rival Athletic Bilbao 1-0 in the delayed 2020 cup final held in Seville.
Barcelona will visit Sevilla on Saturday with the team in third place, five points adrift of leader Atlético Madrid.
Athletic entered this year's semifinals as the favorite against Levante, having already won the Spanish Super Cup in a final against Barcelona after defeating Real Madrid in the semis.
Ivan Rakitic inspires Sevilla to 2-0 win over Barcelona in Copa del Rey semis 1st leg as Messi's 900th game ends in despair.
Barcelona trailed 2-0 going into the 88th minute before Messi helped create goals for Antoine Griezmann and Jordi Alba as the Catalan club kept alive its chance of ending its title drought.
The Argentine scores a goal and sets up another in a 2-1 win over Rayo Vallecano in the round of 16.
Messi has not played in the Copa del Rey this season but coach Ronald Koeman is expected to use him in the round-of-16 game after missing two matches because of a suspension.
Alcoyano scored in the 80th minute to force extra time and again in the 115th to shock the Spanish powerhouse and make it to the last 16.
Teenager Pedro “Pedri” González canceled out Iñaki William’s opener for Bilbao before Messi added two goals to secure an away win for Barcelona that lifted it into third place.
Atletico Madrid will visit Cardassar and Sevilla will play at Ciudad de Lucena in the first round of the Copa del Rey.
It will be the first time the two teams play for the Copa title since Athletic beat Sociedad in 1910 in the deciding match of a three-team mini-tournament.
Real Sociedad reached their first Copa del Rey final in 32 years with a 1-0 victory over second-division side Mirandes.
Mirandes outplayed the hosts for long stretches and equalized in the 41st through striker Matheus Aias. However, Martin Odegaard restored Sociedad’s advantage before halftime.
Real Madrid lost to Real Sociedad 3-4 at home while a late goal from Athletic Bilbao knocked out Barcelona in the quarterfinals of Copa del Rey.
Atletico hadn't been eliminated this early in the Copa since losing to Albacete at this stage in 2011-12, just before it hired coach Diego Simeone.
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