Real Madrid will open their Primera División title defence at home to Valencia, who finished third last season, while the first league Clasico of the new campaign will come on October 7 at the Nou Camp.
Los Blancos ended three years of Barcelona dominance in La Liga by claiming a 32nd league crown last season, during which they set new records for goals scored and points won.
Jose Mourinho's side will, however, open up with a tricky encounter against Los Che who, according to their striker Roberto Saldado, will pose a greater threat to Spain's top two next season.
Barca, meanwhile, face Real Sociedad at home in their maiden league fixture of the new campaign - the first during the tenure of Tito Vilanova, who was promoted following the resignation of Pep Guardiola.
Other highlights from the opening weekend include last term's fifth and sixth best La Liga sides - Levante and Atletico Madrid - meeting in Valencia, while Malaga face newly-promoted Celta Vigo.
Meanwhile, the reverse Clasico fixture will take place at the Santiago Bernabeu on March 3.