The draw for the semi-finals of the Copa del Rey was conducted on Friday.
Athletic Bilbao will take on Valencia, in a game that sees Marcelina face his former club.
Rayo Vallecano, the only team left in the competition that has yet to win the title, play Real Betis in the other tie.
Athletic eliminated holders Barcelona in the round of 16, before defeating Real Madrid 1-0 on Thursday.
Marcelino steered Valencia to Copa del Rey glory in 2019, but was sacked the following season.
In-form Real Betis dumped out city rivals Sevilla, before brushing aside Real Sociedad 4-0 on Thursday.
Rayo reached their first Copa semifinal in 40 years by scraping a 1-0 win against Mallorca.
The first legs will take place on February 9-10 and return matches on March 2-3.
The final will be played on April 23 in Seville.
Copa del Rey semi-final matches confirmed [Full fixtures]