Holders Barcelona will travel to Racing Santander in the last 16 of the Copa del Rey while Real Madrid will meet Albacete after both were drawn against second division opposition on Wednesday.
The other teams involved in the Spanish Super Cup, Atletico Madrid and Athletic Bilbao, also face second-tier opponents.
Tournament rules dictate the Super Cup teams face the lowest ranked teams remaining, until later in the competition.
Atletico will visit two-time winners Deportivo La Coruna, while Athletic go to Cultural Leonesa.
The last 16 matches take place next week, between January 13-15.
Full last 16 draw:
Deportivo La Coruna v Atletico Madrid, Racing Santander v Barcelona, Cultura Leonesa v Athletic Bilbao, Albacete v Real Madrid, Burgos v Valencia, Betis v Elche, Real Sociedad v Osasuna, Alaves v Rayo Vallecano