The LaLiga fixture list for the 2022/2023 season was released by the Spanish Football Federation (RFEF) on Thursday.
Real Madrid will open their campaign with a trip to newly promoted Almeria, while Barcelona are home to Rayo Vallecano.
The two rivals will face off in the first Clasico on the weekend of October 16.
The game on Match Day 9, will be played at Madrid's Santiago Bernabeu stadium, with the return fixture at Barcelona's Camp Nou taking place on the weekend of March 19, 2023.
Atletico Madrid, who finished third last season, begin the season away at Getafe while Sevilla, who finished fourth in the final Champions League spot, will travel to Osasuna.
The 2022/23 LaLiga season will begin on the weekend of August 14, 2022, and end on the weekend of June 4, 2023.