La Liga champions Barcelona will start the defence of the crown with a home clash against Levante on August 18.
Tito Vilanova’s men dominated last season, ending the term 15 points ahead of nearest challengers Real Madrid as they clinched their 22nd domestic title.
They will start their quest for their 23rd at the Camp Nou, with new Brazilian signing Neymar poised to make his league debut against a Levante team which finished 11th last season.
Real begin life under Carlo Ancelotti against Real Betis at the Bernabeu, where Isco could make his bow for the club.
Copa del Rey winners Atletico Madrid travel to Sevilla, while Real Sociedad face Getafe at the Anoeta and two clubs with UEFA Champions League ambitions meet when Valencia welcome Malaga to the Estadio Mestalla.
Newly promoted Almeria and Villarreal face off in Andalusia, and Elche begin their first top-flight campaign for 24 years at Rayo Vallecano.
Celta Vigo, who ensured survival on the final day of last term, start at home to Espanyol, while Basque duo Osasuna and Athletic Bilbao take on Granada and Real Valladolid respectively.
The first Clasico of the season takes place on October 26/27 when Real travel to Camp Nou, with the reverse fixture coming on March 22/23.
Ancelotti’s men meet city rivals Atletico for the first time on September 28/29, and will travel to Estadio Vicente Calderon for the return game on March 1/2.
Valencia take on local rivals Villarreal on October 26/27 and March 22/23, and meet fellow neighbours Levante on January 4/5 and May 10/11.
Sevilla and Betis will fight for local bragging rights on November 23/24 and April 12/13, while Bilbao face biggest rivals Real Sociedad on January 4/5 and May 10/11.
The final round of fixtures takes place on May 18. Barcelona face a tough final encounter against Atletico, and Real welcome Espanyol to the Bernabeu.
Sociedad host Villarreal, Malaga take on Levante and Valencia meet Celta Vigo in three games that could well have implications on the battle for European football, as well as the fight to beat the drop.
Elche’s survival hopes could rest on their last-day trip to Sevilla, while Almeria finish at home against Bilbao.
Elsewhere, Betis travel to Osasuna, Madrid sides Vallecano and Getafe meet and Valladolid will host Granada.