The LFP has announced the fixtures for the new season, with both traditional superpowers set to play each other in the autumn and then in March
Neymar will play in his first Clasico for Barcelona against Real Madrid on October 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 start their title defence with a home match against Levante on the weekend of August 17-19.
Last year's runners-up Real Madrid on the other hand take on Betis at the Santiago Bernabeu in their 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 versus Sevilla and Atletico Madrid.
The first leg of the Supercopa de Espana - the traditional season opener - between Atletico Madrid and Barcelona will take place on August 21 at the Vicente Calderon, with the return at Camp Nou seven days later.