Real Madrid have been handed a tough opening fixture at home to Valencia in their defence of the Primera Division title.
The fixtures were released on Tuesday morning and the opening weekend, on August 18 and 19, sees Jose Mourinho's men pitted against Los Che.
Valencia finished third in La Liga last season and will be led by former Liverpool defender Mauricio Pellegrino who replaced Unai Emery as coach in May.
Tito Vilanova's first league game in charge of Barcelona following Pep Guardiola's decision not to extend his contract will be a visit to Real Sociedad.
The first El Clasico of the league season will take place on the weekend of October 6/7 at the Nou Camp with the return at the Bernabeu scheduled for March 2/3.
In the other opening weekend fixtures, Sevilla host Getafe, Atletico Madrid go to Levante and Athletic Bilbao begin what is expected to be their final season at San Mames by hosting Real Betis.
Of the three promoted sides, Celta Vigo face a daunting opener against Malaga, Deportivo La Coruna host Osasuna and Real Valladolid visit Real Zaragoza.
Espanyol's trip to Mallorca and Rayo Vallecano's home game against Granada make up the full opening weekend's matches.