A brilliant hat-trick from Charles gave Malaga their first win of the league season as their 10 men beat David Moyes' Real Sociedad 3-1 at home.
The former Celta striker scored twice in the opening seven minutes, including a spectacular opener before Imanol Agirretxe got a goal back for the visitors.
Moyes' hopes of a much-needed result were boosted when Fernando Tissone received a second yellow card, but were then dashed by Charles' 89th-minute strike. The defeat leaves struggling Real with just six points from their opening seven fixtures.
Eibar's impressive start to the campaign continued with a 2-0 win at relegation candidates Las Palmas, with the goals coming from Saul Berjon and Borja Baston.
On-loan Barcelona youngster Alen Halilovic scored in Sporting Gijon's 2-1 victory away to Espanyol.
Alex Menendez's last-gasp goal sealed the points after Felipe Caicedo had cancelled out Halilovic's opener.
In Saturday's other game, Deportivo La Coruna were held to a 1-1 draw at Granada. The away side had taken the lead through Faycal Fajr, but Piti's equaliser stalled their positive run of form.