Celta de Vigo
Neymar will play in his first Clasico for Barcelona against Real Madrid on Oct. 27 at Camp Nou.
The second clash of the 2013-14 campaign between Spain's two superpowers is set for a March 23 date at the Santiago Bernabeu.
Meanwhile, Barca starts its title defense with a home match against Levante on the weekend of August 17-19.
Last year's runner-up, Real Madrid, takes on Betis at the Santiago Bernabeu in the club's first league game under new head coach Carlo Ancelotti.
The other standout ties of matchday one are the game between Valencia and Malaga and the match that sees Sevilla and Atletico Madrid face off.
The first leg of the Supercopa de Espana - the traditional season opener - between Atletico Madrid and Barcelona will take place on Aug. 21 at the Vicente Calderon, with the return at Camp Nou seven days later.