Atletico Madrid failed to build on Wednesday's notable Champions League success against Juventus when they were beaten 3-1 at a resurgent Valencia in La Liga on a day of records for leaders Barcelona.
Valencia's stirring victory at their Mestalla stadium briefly lifted them to the top of the table before in-form pair Lionel Messi and Neymar struck in a 2-0 triumph at Rayo Vallecano, who had two players sent off, to restore Barca's two-point lead.
The Catalan club are the first La Liga team to avoid conceding a goal in their opening seven matches of the season.
Valencia started the campaign in impressive form and made a thrilling start at the Mestalla to race into a 3-0 lead by the 13th minute.
Atletico centre back Miranda put through his own net in the sixth minute, Andre Gomes finished superbly after a fine run a minute later and Nicolas Otamendi nodded in at a corner to leave the champions reeling.
Mario Mandzukic pulled a goal back in the 29th minute when he followed up a Tiago effort to head home before Atletico squandered a chance for a second on the stroke of halftime.
Valencia have 17 points from seven matches, with unbeaten Barca on 19.
Atletico have 14 points in third and can be overtaken by Real Madrid, Sevilla and Celta Vigo if they all win on Sunday.