Barça were in the draw thanks to a 6-1 thrashing of Sevilla after losing the first leg 2-0 at the Sanchez-Pizjuan.
Then they will make a trip to face their nosy neighbours Atletico Madrid on 9 February, before flying to Amsterdam on 11 February to play the first leg of their Champions League tie against Ajax.
Madrid defeated Girona 4-2 at Bernabeu and 3-1 away in both legs of the quarter finals resulting to a 7-3 aggregate scoreline.
"There's nothing like it", Real Madrid director Emilio Butragueno said.
Two-time cup winners Real Betis will host Valencia in the opening leg of the other semifinal with the second game played on February 27 at the Mestalla stadium. "We are talking about two teams with a lot of resources, with extraordinary players, and we always expect very tight games".
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"We trust our players but obviously this is one of the greatest games in the world today".
The El Clasico will hold over two legs as Los Blanocs will be looking to unseat La Blaugrana as champions over the last four years.
The final will take place on May 25 at Betis' home ground, the Estadio Benito Villamarín.
Valencia are back in the semifinals for the first time since 2012 after a 3-2 aggregate win against Getafe.They last won the Cup in 2008.
Real Madrid's upcoming fixture list does not paint a prettier picture.