Goalkeeper Jaume Domenech's heroics in the penalty shootout allowed Valencia to prevail over Alaves and claim a spot in the Copa del Rey semi-finals.
In a mirror image of Valencia's 2-1 win in the first leg, the second leg ended with Alaves up 2-1 here on Wednesday, reports Efe.
All three goals came in the final 18 minutes of regulation.
Two minutes after coming on as a substitute, Munir put the hosts on the board with a thunderous header in the 72nd minute. Valencia equalised five minutes later as Santi Mina exploited a poor clearance by Rodrigo Ely, who had an assist on the Alaves goal.
Alaves pulled ahead again in the 86th minute when Ruben Sobrino fired in the rebound after Domenech made the initial stop on a Munir free kick.
The visitors flew forward to settle the contest in regulation, but Alaves defended tenaciously and keeper Antonio Sivera thwarted Simone Zara's effort in the final seconds to preserve the hosts' dream of a comeback.
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Extra time was subdued compared with the frantic final minutes of regulation as both teams had already used all three substitutions and fatigue was taking its toll.
Domenech made two stops during the shootout and Sobrino fired wide, giving Valencia a 3-2 advantage and the win.
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