The two giants will first meet in the Catalan capital on the weekend of October 27-28, following both sides' involvement in the third Champions League group game. Meanwhile, the Bernabeu fixture will be held on the first weekend of March.
The 2018-19 La Liga fixtures were announced on Tuesday, with Atletico Madrid, who finished second last season, travelling to fourth-placed Valencia in the pick of the opening day's games.
Champions Barcelona will host Basque outfit Alaves, while Real Madrid have a home tie against Getafe when the season kicks off on the weekend of August 18-19.
Following public comments from La Liga chief Javier Tebas, who said it was "not ideal" for the second El Clasico meeting between Real and Barca last season to be played with the latter having already won the league title, the two sides will face off earlier this campaign.
The two giants will first meet in the Catalan capital on the weekend of October 27-28, following both sides' involvement in the third Champions League group game. Meanwhile, the Bernabeu fixture will be held on the first weekend of March.
Real will host local foes Atletico at the end of September in the seventh match of the season, travelling across the city for the second meeting of the season on the weekend of Feb. 9-10.
Other notable opening weekend fixtures see Villarreal host Real Sociedad, top division debutants Huesca visit Eibar and Celta Vigo take on Espanyol.