Following on from their opening day 6-0 mauling of Real Zaragoza, Madrid were again amongst the goals as they downed Getafe 4-2 at the Bernabeu.
Karim Benzema bagged a brace while Cristiano Ronaldo, taking his tally to 15 goals in his last six league games with a controversial penalty on the hour mark, and substitute Gonzalo Higuain were also on target for Jose Mourinho's men.
Miku netted a cool double for Getafe but it was not enough to prevent his side slipping to defeat.
Barca also began their campaign in style with a 5-0 thrashing of last season's fourth-placed side Villarreal and another one-sided match looked on the cards tonight as goals from Xavi and Cesc Fabregas put them 2-0 up at Sociedad with only 11 minutes on the clock.
However, Sociedad, who were the only side to beat Barca on their travels last season, hit back to share the points with two goals in three second-half minutes from Imanol Agirretxe and Antoine Griezmann.
To add injury to insult for Pep Guardiola's men, they also lost big-money summer signing Alexis Sanchez to a hamstring tear in the first half which could rule the Chile international out for up to two months.
Valencia joined Mourinho's side on six points after defeating big-spending Atletico Madrid 1-0 at the Mestalla in tonight's late game.
Roberto Soldado, who scored a hat-trick and an own goal in Valencia's opening-day 4-3 win over Racing Santander, headed in the only goal of the game in the 52nd minute.
Atletico gave a debut to 40million euro record signing Radamel Falcao but the prolific Colombian failed to find the breakthrough to leave the Rojiblancos without a goal from two games.
In this evening's other game, Villarreal and Sevilla shared a 2-2 draw at El Madrigal - with the home side unlucky not to take all three points despite playing with a man less for more than an hour.
In-form striker Alvaro Negredo gave Sevilla the lead after home goalkeeper Diego Lopez had been sent off for a foul on Diego Perotti in the 21st minute.
Negredo's resulting penalty was saved by Villarreal replacement goalkeeper Cesar Sanchez but the Spain international fired home the rebound for his fifth goal in three games for club and country.
The Yellow Submarine were awarded a penalty of their own 12 minutes later and Giuseppe Rossi made no mistake from the spot, and then Marco Ruben put the home side ahead with a fine finish 18 minutes from time.
The hosts were denied the win, though, when Alexis headed home an 87th-minute free-kick.