Barca's arch-rivals Real Madrid, whose last title came in 2008, host Athletic Bilbao, and Valencia, who finished third last season, play at Osasuna, the RFEF said after the draw was made at their headquarters outside Madrid.
The season-opening Spanish Super Cup between La Liga champions and holders Barca and King's Cup winners Real will be played over two legs on August 14 and August 17.
The first leg will kick off at Real's Bernabeu stadium at 10pm local time and the return leg at the Nou Camp will start at 11pm.
The pair are due to meet in the league for the "Clasicos" on December 10/11 in Madrid and April 21/22 in Barcelona, although the match at the Bernabeu may have to be rescheduled because of Barca's participation in the FIFA Club World Cup.
Fixtures:
Opening weekend (August 20/21)
Osasuna v Valencia
Real Sociedad v Atletico Madrid
Villarreal v Sporting Gijon
Malaga v Barcelona
Real Betis v Sevilla
Espanyol v Granada
Real Vallecano v Real Mallorca
Real Madrid v Athletic Bilbao
Levante v Real Zaragoza
Racing Santander v Getafe
Matchday 2 (August 27/28)
Valencia v Racing Santander
Atletico Madrid v Osasuna
Sporting Gijon v Real Sociedad
Barcelona v Villarreal
Sevilla v Malaga
Granada v Real Betis
Real Mallorca v Espanyol
Athletic Bilbao v Real Vallecano
Real Zaragoza v Real Madrid
Getafe v Levante
Matchday 3 (September 11/12)
Valencia v Atletico Madrid
Osasuna v Sporting Gijon
Real Sociedad v Barcelona
Villarreal v Sevilla
Malaga v Granada
Real Betis v Real Mallorca
Espanyol v Athletic Bilbao
Real Vallecano v Real Zaragoza
Real Madrid v Getafe
Racing Santander v Levante
Full fixtures here
