While, Real Madrid were held by Real Betis in a goalless affair after Barcelona lost 3-1 to Levante, Atletico Madrid and Sevilla wasted their chance to leap to the top of the table when they drew 1-1 in Seville.
Real Madrid has yet to win a match in Group A this season. A third straight setback could leave the team in danger of not making it out of the group stage of the Champions League for the first time since the 1989-90 season.
Political unrest in Spain's Catalonia region has thrown the blockbuster clash between Barcelona and Real Madrid into doubt as reports emerged that the match will now be played in December instead of the scheduled date - October 26.
Real Madrid and Barcelona are set to clash for the first El Clasico of the season on October 26, but the Spanish authorities have asked to relocate the venue from Camp Nou owing to the growing protests in Catalonia.
Real Madrid beat Manchester United 2-1 to lift the UEFA Super Cup on Tuesday. Casemiro, Isco scored for the Spanish side while Romelu Lukaku scored the only goal for Manchester United in his debut match.