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The big game Sunday sees Valencia at home to Sevilla.
Valencia, who finished sixth last season, remain in financial and institutional chaos. However, they have managed to hold on to star strikers David Villa, David Silva and Juan Mata, though they have hardly made any signings at all.
Sevilla, for their part, have spent heavily on Alvaro Negredo, Didier Zokora and Sergio Sanchez and are aiming to do even better than last season, when they finished third.
Also Sunday, Atletico Madrid - who cruised into the Champions League against Panathinaikos on Tuesday - will start away to Malaga, whilst Villarreal are away to Osasuna.
Sunday's other games are as follows: Racing Santander-Getafe, Almeria-Valladolid, Mallorca-Xerex and Athletic Bilbao-Espanyol.
The first round of matches will not finish until Monday, because Barcelona's home game against Sporting Gijon has been put back due to their participation in Friday's European Supercup showpiece against Shakhtar Donetsk in Monte Carlo.
Barca will again be without injury victims Andres Iniesta, Rafa Marquez and Gabriel Milito.
Many Barca fans are worried about the club's lack of signings. So far, only Zlatan Ibrahimovic and Maxwell have arrived, both from Inter Milan.
Club president Joan Laporta hopes to clinch the signing of Shakhtar defender Dmytro Chygrynskiy in Monte Carlo, in order to finally placate coach Josep Guardiola, who has been asking for the Ukrainian defender all summer.