Santi Mina’s header put Valencia ahead after eight minutes and Álvaro Negredo slotted home having been played in by André Gomes after 31 minutes.
Neville, in his third match in charge, decided against making too many changes despite a 3-1 lead from the first leg against the third-tier side.
Eibar overturned a 3-0 first-leg loss as a Mikel Arruabarrena penalty completed a 4-0 win over 10-man Ponferradina. The top-flight side showed their priority was La Liga by resting nine players from the team that drew with Valencia on Sunday and still won, although the first-half dismissal of Jesus Berrocal made a big difference.
Mirandes of the second tier knocked out Malága as Lago Junior’s goal secured a 1-0 win on the night and 3-1 aggregate triumph.
Óscar De Marcos hit a first-half opener as Athletic Bilbao hammered Linense 6-0 and went through 8-0 on aggregate.
Rayo Vallecano advanced on goal difference against Getafe after losing 3-1, having won the first leg 2-0 while Las Palmas knocked out Real Sociedad after a 1-1 draw put them through 3-2 on aggregate.
Barcelona had reached the last 16 after beating Villanovense in a tie brought forward due to their participation in the Club World Cup. Real Madrid were thrown out of the competition having fielded an ineligible player in their first-leg game against Cádiz.
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