Barcelona eased past Segunda B minnows Cultural Leonesa, while Valencia earned a 1-0 win over third division CD Alcoyano.
Holders Barcelona have one foot in the next round after picking up a 2-0 win in the first leg of their Copa del Rey tie against Cultural Leonesa in Leon.
Barcelona coach Pep Guardiola rested most of his top stars, but there was still a number of regular faces in his starting line-up including Yaya Toure, Seydou Keita, Bojan Krkic and Pedro.
Pedro was the hero for Barca as he grabbed both goals to make the second leg a mere formality.
Pedro broke the deadlock for Barca four minutes before the break and the highly-rated youngster added a second just past the hour mark.
Valencia earned a 1-0 first leg win over third division CD Alcoyano in the fourth round of the Copa del Rey.
Joaquin scored the only goal of the game early on to give Valencia an advantage to take to the second leg at La Mestalla.
Deportivo La Coruna overcame Segunda Liga side Real Murcia 1-0 courtesy of Alberto Lopo's strike
Segunda Liga side Rayo Vallecano shocked Athletic Bilbao 2-0 to put them in pole position to reach the next round.
Celta Vigo upset Tenerife with a 2-1 home success and fellow Segunda Liga outfit Hercules picked up a 2-1 success over Almeria.
Getafe secured a 2-0 win over Espanyol thanks to second-half goals from Juan Angel Albin and Jaime Gavilan.
Osasuna put themselves in control of their tie with Xerez thanks to a 2-1 away first-leg success.
Sergio and Dady were on the mark for Osasuna with Giancarlo Maldonado finding the net for Xerez.
Malaga earned a 1-1 draw with fellow La Liga side Real Zaragoza as Apono's penalty cancelled out Angel Lafita's opener for Zaragoza.
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