The Catalan giants led 3-0 from the first leg, but Alaves’ Borja Viguera sparked vague hopes of a comeback at the Nou Camp with a goal in the 16th minute.
But Adriano equalised in the 35th minute, leaving Villa to settle the tie in the second half and the Spain striker duly notched in the 56th minute before doubling up three minutes later.
Atletico Madrid had also enjoyed an easy run-out in their first-leg meeting with Jaen, winning 3-0, but the Andalusian minnows would only concede once at the Vicente Calderon.
With Radamel Falcao rested, Raul Garcia assumed goalscoring duties in the 16th minute and Atleti claimed a 4-0 aggregate victory.
Diego Perotti opened the scoring from the penalty spot after Javi Lopez saw red in the 25th minute and it was plain sailing for Michel Gonzalez’s men from then on.
Ivan Rakitic and Baba Diawara registered a goal apiece either side of half-time and Sevilla were comfortably through to the next round.
Valencia turned a 2-0 victory over Llagostera last time out into a 5-1 aggregate win as Adil Rami (15) and Bernat (78) made their mark at the Mestalla.
Substitute Jose Wilfred (57) had contributed an own goal in between times, but Rubio Nico gave the visitors some reason to be cheerful six minutes from time.
Levante overturned a 1-0 deficit to run out 4-2 aggregate winners over Melilla, with Nikos Karabelas (25), Roger (62) and Michel (76) all getting among the goals.
Mustafa Chota had given Melilla a chance of victory with his 27th-minute goal, but substitute Vicente Iborra put Levante out of sight with a penalty five minutes from time, before Michel was sent off.
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