Lionel Messi could not get a goal to mark the birth of his first son but Barcelona took the points in a straightforward 3-1 victory over Celta Vigo which moved them three points clear of Atletico at the summit.
• Blog: A record Blaugrana win
• Blog: Mourinho's quick-fire century
Three goals in the space of five minutes sparked the first half into life after the 20-minute mark as Adriano and David Villa scored either side of Mario Bermejo's strike, though Adriano then limped off injured before half time. Jordi Alba wrapped up the win just after the hour mark.
The breakthrough came when Pedro crossed from the right for Adriano to slot home. Celta Vigo's reply was immediate, with Valdes unable to hold Fernandez Augusto's shot and Bermejo sweeping home the rebound.
But just as quickly as Celta equalised, Barca retook the lead, with Iniesta's pass finding Villa for the finish. Victory was assured when Villa turned provider to play the ball through for Jordi Alba to score from close range.
Real Madrid moved into third place and handed Jose Mourinho his 100th win in charge of Los Blancos with a 4-0 victory over Real Zaragoza.
Gonzalo Higuain and Angel Di Maria put the hosts in a commanding position with a goal apiece in a two-minute spell midway through the first half but Zaragoza were unfortunate not to get back into the game early in the second period as Jose Mari fired a shot off the crossbar and Helder Postiga had a goal wrongly ruled out for offside.
However, Madrid wrapped things up in the final two minutes as both Michael Essien and Luka Modric scored their first goals since swapping the Premier League for the Spanish capital.
Valencia survived the dismissals of Ricardo Costa and two of their coaching staff to inflict a first defeat of the season on Atletico Madrid as they ran out 2-0 winners.
Roberto Soldado's stunning opener gave the hosts an interval lead and Nelson Valdez rounded off a 2-0 victory in stoppage time.
Costa was dismissed in the 90th minute for a second booking and coach Mauricio Pellegrino and his assistant Carlos Compagnucci were sent from the dug-out in separate incidents, but it was Valencia's day nonetheless.
Rayo Vallecano inflicted Malaga's first home defeat of the season, 2-1, thanks to two goals by Piti.
The midfielder opened the scoring from Leo Baptistao's driven cross on 11 minutes but after squandering a number of chances towards the end of the first half, the visitors were pegged back four minutes into the second period as Martin Demichelis headed home Joaquin's free-kick.
Rayo responded brilliantly to conceding and after a sustained spell of pressure, they got the winner they deserved on the hour mark when Leo again teed up Piti to fire into the bottom corner for his fourth goal of the season.