The opening fixture in the rivalry will take place at Camp Nou on October 24, 10 games into the new campaign, with the returning meeting to be held at the Santiago Bernabeu on March 20 next year.
It remains to be seen whether Barca, who will start their season at home to Real Sociedad on the weekend of August 14-15, will still be able to call on Lionel Messi, whose contract with the Catalan club runs out at the end of June.
The 34-year-old is yet to commit to a new deal, though Barca president Joan Laporta has stressed his confidence an agreement will be reached.
Madrid, meanwhile, kick off their season on the road against Deportivo Alaves. Los Blancos requested an away fixture to start 2021-22 as redevelopment work continues at their Bernabeu home, meaning Carlo Ancelotti will have to wait a little longer for his first home match since returning to the Spanish club.
Meanwhile, reigning champions Atletico Madrid will start their title defense away at Celta Vigo.
The first Madrid derby, to be hosted by Los Blancos, will take place in December, with the second fixture – a potential title decider – scheduled for May 8.
Barca will close out their season at home to Villarreal, with Madrid hosting Real Betis and Atleti travelling to Real Sociedad.
Wednesday also saw confirmation of the date for the Copa del Rey final, which will take place at Estadio de la Cartuja in Seville on April 23 next year.
Barring the last two matchdays, the entirety of the 2020-21 season had to be played behind closed doors due to the ongoing impact of the coronavirus pandemic.
Spanish health minister Carolina Darias confirmed earlier this month that fans would be allowed to return for games in the new campaign, though the emergence of the Delta variant across Europe may put those plans on hold.
LaLiga president Javier Tebas, however, insisted last week that he hopes stadiums will be back at full capacity by November.
Speaking on June 23, Tebas said:
“I believe we can start the season with 60 per cent capacity. Some areas of Spain will have more, some less. But by November or December we should be at 100 per cent.”
La Liga 2021-22 opening day fixtures:
Barcelona v Real Sociedad
Cadiz v Levante
Celta Vigo v Atletico Madrid
Deportivo Alaves v Real Madrid
Elche v Athletic Bilbao
Osasuna v Espanyol
Real Mallorca v Real Betis
Sevilla v Rayo Vallecano
Valencia v Getafe
Villarreal v Granada