Spanish international Denis Suarez bagged a double as Barca beat third-tier Leonesa 4-1 to progress 5-1 on aggregate.
Atletico were too strong for Sant Andreu, brushing aside the fourth division minnows 4-0 for a 5-0 aggregate win.
It was a red letter evening for Villarreal’s Cameroon striker Karl Toko-Ekambi, who scored a four times in his side’s 8-0 thumping of Almeria, after a first leg that ended all square at 3-3.
Another La Liga outift Sevilla also went through to join Valencia and Espanyol, who assured their progress on Tuesday.
On Thursday Real Madrid host Melilla, their third-division visitors from North Africa who have a mammoth task of overturning a 4-0 first leg loss in what was coach Santiago Solari’s first game in charge for the European champions.
Other top flight clubs in action are Levante, Eibar, Athletic Bilbao and Real Betis.
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