Athletic Club head coach Marcelino will face his former club Valencia in the Copa del Rey semi-finals. (Live stream on ESPN+ Feb. 9)
Rayo Vallecano, the only team remaining in the competition who have yet to win the title, were drawn against Real Betis in the other draw.
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Athletic, who have lost in the final in the previous two editions, knocked out holders Barcelona in the round of 16 before beating Real Madrid 1-0 on Thursday.
Marcelino guided Valencia to Copa del Rey glory in 2019 but was dismissed the following season.
Valencia knocked out relegation-threatened Cadiz.
In-form Real Betis, third in La Liga, knocked out city rivals Sevilla before ousting Real Sociedad in San Sebastian 4-0 on Thursday.
Rayo reached their first Copa semi-final in 40 years by winning 1-0 against Mallorca.
The Madrid outfit have been among the surprises in La Liga and are eighth in the table.
The first legs will take place on February 9 and 10 and the return matches on March 2 and 3.
The final will be played on April 23 in Seville.
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