The duo will face off at 5pm UK time at the Camp Nou.
Should Barca go into the game having defeated Osasuna on Week 9, then they will have the chance to beat Real Madrid’s own record from 1968-69 for the best start to a League season, if they defeat Los Blancos.
Carlo Ancelotti’s side will have a day less of rest for the fixture, with La Blaugrana in Champions League action against Milan on the Tuesday evening and Madrid playing Juventus on the Wednesday before the weekend.
Meanwhile, the Valencian derby between Villarreal and Valencia will take place on the Sunday early evening, whilst Atletico Madrid will host Real Betis later that same evening.
Rayo Vallecano kick things off for the weekend by hosting Real Valladolid on the Friday night, whilst Monday will see Getafe close things out against Athletic Bilbao.
Week 10 kick-offs (UK time)
Friday October 25
Rayo Vallecano-Valladolid, 8pm
Saturday October 26
Barcelona-Real Madrid, 5pm
Sunday October 27
Real Sociedad-Almeria, 6pm
Monday October 28