Athletic Bilbao secured their first La Liga win of the season with a 1-0 victory over Valencia on Wednesday night.
Benat Prados fired Bilbao in front just before the break, with defeat leaving Valencia pointless at the foot of the table.
Atletico Madrid were held to a frustrating 0-0 draw with Espanyol.
Rodrigo Riquelme had a goal chalked off by VAR in the second half with neither side able to break the deadlock but a point sees Atletico move into fourth in the table.
Alaves earned their maiden win of the campaign after beating Real Sociedad 2-1.
Sociedad were reduced to 10 men in the 29th minute when Mikel Oyarzabal was shown a straight red card, but they then took the lead four minutes later through Brais Mendez.
However, Alaves equalized in the fifth minute of first-half stoppage time when Asier Villalibre slotted home from the spot.
Toni Martinez then found the winner for the visitors in the 77th minute.
Elsewhere Valladolid and Leganes shared the spoils with a goalless draw.