Real Madrid and Athletic Bilbao maintained their 100 per cent starts to the season with victories on Sunday.
Cristiano Ronaldo helped himself to two goals as Real Madrid overcame newly-promoted Xerez 5-0 at El Santiago Bernanbeu.
Real got off to a flying start with Ronaldo firing them in front in the very first minute with a shot from the edge of the box.
The home side had to wait until 15 minutes from time for a second goal as Ronaldo headed home from a corner.
Guti netted a third on 78 minutes with a clinical finish and Karim Benzema made it 4-0 eight minutes from time with his first goal for the club since his summer arrival from Lyon.
Ruud van Nistelrooy came off the bench to score his first goal since his return from injury and send Real to the top of the table on goal difference.
Athletic Bilbao maintained their perfect start to the campaign with a thrilling 3-2 win over Villarreal.
Fernando Llorente put Bilbao in the driving seat with two goals in the first half.
Cani pulled a goal back for Villarreal four minutes after the break, but Javi Martinez restored the two-goal cushion just before the hour mark
Santi Cazorla reduced the arrears five minutes from time with a superb free-kick, but Bilbao held on for the win to join Barcelona and Real Madrid on nine points at the top of the table.
Valencia missed the chance to keep pace with the leading pack after ten-man Sporting Gijon ended their 100 per cent start with a 2-2 draw at La Mestalla.
David Barral gave Sporting a shock lead after just seven minutes, but David Villa drew Valencia level on 24 minutes against his former club.
Things got worse for Sporting when Michel was sent off on 26 minutes for a second bookable offence.
Villa fired Valencia in front on the hour mark with a superb curling effort from the edge of the box.
Sporting grabbed an unlikely leveller four minutes from time when defender Gregory headed home from close range.
Almeria picked up their first win of the season with a 1-0 success over Getafe.
Michel scored the only goal of the game three minutes after the break to move Almeria into seventh spot.
Real Valladolid shocked Real Zaragoza 2-1 to earn their first victory of the season.
Marcos Garcia gave Valladolid the perfect start with the opener after just four minutes only for Jorge Lopez to draw Zaragoza level on 27 minutes.
Sisi netted the winner for Valladolid on 56 minutes to move them up to eighth in the table.
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