Real Madrid will open the defence of its Primera Division title at home to Valencia.
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 after Pep Guardiola's decision not to extend his contract, visits Real Sociedad.
Sevilla hosts Getafe, Atletico Madrid goes to Levante and Athletic Bilbao, whose coach Marcelo Bielsa has returned to work after speculation he was to quit after leading it to the final of the Europa League and Copa del Rey last season, takes on Real Betis at San Mames.
Celta Vigo has arguably the toughest opening of the three promoted sides with a clash against big-spending Malaga. Deportivo La Coruna hosts Osasuna and Real Valladolid visits Real Zaragoza.