Villarreal continued their unbeaten start to the Primera Division season as they claimed a 2-1 victory over Espanyol.
Jeremy Perbet fired the hosts into a first-minute lead and Jonathan Pereira doubled that midway through the second half.
Sergio Garcia grabbed one back for Espanyol but they could not grab an equaliser as they slipped to their first defeat of the season.
Athletic Bilbao fought back from a goal down to continue their strong start to life under Ernesto Valverde with a 2-1 victory over Real Betis at the new San Mames.
The Basque side spurned a penalty opportunity when Benat Etxebarria failed to convert from the spot, and they fell behind just after the hour when Jorge Molina tapped in from a corner.
But Oscar de Marcos headed in an equaliser before Mikel San Jose grabbed the winner with eight minutes to go to make it four wins from six under former Valencia boss Valverde.
In Thursday's remaining game, Getafe leapfrogged their opponents as they beat Celta Vigo 2-0. Lisandro Lopez and Alvaro Arroyo scored in a six-minute spell either side of half time as the home side moved a point clear of their visitors in the table.
Celta have now gone four games without a win and remain with just a single victory this term.