The other quarter-final played on Wednesday pitted the last two cup winners against each other as Valencia entertained Sevilla in their Mestalla stadium.
In contrast to the Barcelona derby, the two teams produced 90 minutes of thrilling Cup football as Valencia scored two late goals to win 3-2.
The home side took an early lead through top scorer David Villa, but after Villa limped off midway through the first half, Sevilla grew in confidence.
Brazilians Luis Fabiano and Adriano, the latter from a clear offside position, scored in the second half to put the visitors 2-1 ahead and it looked as if Sevilla had one foot in the semi-finals.
However, Valencia dug deep and in the last 10 minutes goals from Ruben Baraja and Juan Mata gave them a nail-biting win.
A single goal in next week's return leg would be enough to qualify Sevilla, but if that game is as exciting as this, there can be no clear favorite.
The remaining quarter-finals between Athletic Club Bilbao and Sporting Gijon and between Mallorca and Betis are to be played on Thursday.
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