Carlo Ancelotti will begin his reign as Real Madrid coach in La Liga at home to Real Betis, while Barcelona begin their league campaign against Levante at the Camp Nou, meaning Neymar will play his first game in the Spanish top flight in front of his new club's fans.
Barça host Madrid in the first Clásico of the season, on 27 October, while the second fixture between Spain's biggest two clubs will take place on 23 March.
The season begins on the weekend of 17 August, and ends on 18 May, earlier than usual, because of the World Cup in Brazil.
Opening day fixtures for season 2013-14
Real Madrid-Real Betis