Jose Mourinho’s side finished the 38-game campaign with 100 points to unseat Barcelona as kings of Spain, and will face a tough challenge at the Bernabeu on the opening day in the form of third-placed Valencia - who finished 39 points behind Madrid last season.
Runners-up Barca also get the league campaign underway on home turf, welcoming Real Sociedad to Camp Nou for new manager Tito Vilanova's Liga bow, while fourth-placed Malaga travel to newly-promoted Celta Vigo.
Deportivo La Coruna, also making their return to the top flight, host Osasuna while Europa League winners Atletico Madrid are away to Levante and runners-up Athletic Bilbao are at home to Real Betis.
Real Valladolid, who claimed the third and final promotion berth via the play-offs, travel to Real Zaragoza on the opening weekend, set for the August 18 and 19.
The first Clasico of the season between Barcelona and Real will take place on the weekend of October 7 at Camp Nou with the reverse fixture on the weekend of March 3.
The two giants and great rivals also meet over two legs next month in the Spanish Super Cup, the traditional season opener that pits the league champions (Real) against the Copa del Rey winners (Barca).
LA LIGA OPENING MATCH DAY FIXTURES
Athletic Bilbao v Real Betis
Sevilla v Getafe
Real Zaragoza v Real Valladolid
Real Madrid v Valencia
Levante v Atletico Madrid
Barcelona v Real Sociedad
Celta Vigo v Malaga
Mallorca v Espanyol
Rayo Vallecano v Granada
Deportivo la Coruna v Osasuna