Real Madrid will begin the defence of their Primera Division title at home to Valencia while Barcelona, runners-up last season, are in action against Real Sociedad.
The fixtures for the 2012-13 season were released on Tuesday morning and the opening weekend, on August 18 and 19, sees Jose Mourinho's men pitted against Los Che, who finished third last season and appointed Mauricio Pellegrino to replace Unai Emery as coach in May.
Barcelona, now under Tito Vilanova following Pep Guardiola's decision not to extend his contract, visit Sociedad, who ended 2011-12 in 12th place.
Sevilla host Getafe, Atletico Madrid go to Levante and Athletic Bilbao, whose coach Marcelo Bielsa has returned to work after speculation he was to quit after leading them to the final of the Europa League and Copa del Rey last season, take on Real Betis at San Mames.
Celta Vigo have arguably the toughest opening of the three promoted sides with a clash against big-spending Malaga. Deportivo La Coruna welcome Osasuna and Real Valladolid visit Real Zaragoza.
The season's first El Clasico will take place on the weekend of October 6/7 at the Camp Nou with the return at the Bernabeu scheduled for March 2/3.