Both sides played out a 1-1 draw at Santiago Bernabeu on Saturday evening in a game where neither side really went all out for victory.
However, the stakes are a lot higher on Wednesday than they were at the weekend as the winner of the clash in Valencia will take home the Copa del Rey.
Mourinho's Madrid will be desperate to make amends for the humiliating 5-0 La Liga loss at Camp Nou earlier this season and history shows that they have every chance of beating Barcelona at the Mestalla.
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Apr 16: La Liga
9pm BST - Bernabeu
Apr 20: Copa Del Rey final
9pm BST - Mestalla, Valencia
Apr 27: Champions League semi, 1st leg
7.45 BST - Bernabeu
May 3: Champions League semi 2nd leg
7.45 BST - Nou Camp
The match that Madrid will be of particular interest is the final of 1974. The Whites were hammered 5-0 by the Catalans earlier in the season as Juan Manuel Asensi (2x), Johan Cruyff, Juan Carlos and Hugo Sotil all found the net to help Barca to an impressive victory at Santiago Bernabeu.
Nevertheless, things were completely different when both sides met again in the final of the Copa later in the season. Barcelona had to make do without players such as Cruyff and Sotil due to regulations on foreign players at the time, and Real Madrid got their revenge as they thrashed Barca 4-0 courtesy of goals from Santillana, Benito Rubinan, Francisco Aguilar and Pirri.
It remains to be seen whether Madrid will again be able to produce a similar scoreline on Wednesday evening, but head coach Jose Mourinho and his men will be encouraged to to know that history is on their side.
Wednesday's match kicks off at 21:00 BST in Valencia.