Athletic Bilbao picked up their first LaLiga win of the season after beating Valencia 1-0.
Benat Prados fired Bilbao in front just before the break, with defeat leaving Valencia without a point at the foot of the table in Spain's top-tier competition.
Atletico Madrid were held to a frustrating 0-0 draw with Espanyol on Wednesday (Thursday AEST).
Rodrigo Riquelme had a goal chalked off by VAR in the second half with neither side able to break the deadlock, but a point moved Atletico into fourth place in the standings.
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 took the lead four minutes later through Brais Mendez.
However, Alaves equalised 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.
