Villarreal's difficult start to the La Liga season continued as they were beaten 1-0 at home by Girona on Friday.
Cristhian Stuani scored his first goal of the season early in the second half and it proved to be enough to give Girona their first victory of the campaign.
Substitute Charles scored in stoppage time to give Eibar their first win of the season with a 2-1 victory against Real Sociedad.
Willian Jose, who scored in Sociedad's opening-day win at Villarreal, was on target again after 15 minutes to give his side an early lead. However, the visitors were not in front or long as Marc Cardona equalised with 26 minutes on the clock.
Neither side really threatened a winning goal and the match looked destined for a draw until Charles, on for Cardona, headed home a Joan Jordan cross.
It inflicted a first loss of the season on Sociedad while Eibar got their first points on the board after beginning the campaign with defeats to newly-promoted Huesca and Getafe.
Newly-promoted Real Valladolid are still looking for their first goal in La Liga this season after a 0-0 draw at Getafe. It was a game of very few chances at the Coliseum Alfonso Perez.