The round of matches kicks off on Friday night when Celta Vigo look to confirm the improvement they showed in their first two games under new coach Oscar Garcia at home to Real Valladolid, reports Xinhua news agency.
Last weekend saw Celta win 3-1 away to Villarreal and this will be Oscar's first game in charge at the Balaidos stadium.
Real Madrid travel to Vitoria to take on an Alaves side that has only suffered one home defeat so far this season.
Zinedine Zidane's men produced some of their best football this campaign in their midweek 2-2 draw at home to Paris Saint-Germain, but will be without the injured Eden Hazard, and Zidane will have to consider whether to start Gareth Bale, Rodrygo or Isco in place of the Belgian winger.
A point in Vitoria would put Madrid top of the table and put the pressure on Barcelona ahead of their visit to Atletico Madrid on Sunday night.
Barca's away form has been poor this season as they showed in their struggles to beat Leganes last weekend, and Atletico will test their resolve to the limit.
Ernesto Valverde's men improved drastically in their 3-1 win at home to Borussia Dortmund on Wednesday as Lionel Messi, Luis Suarez and Antoine Griezmann all scored, and Sunday's game will be Griezmann's first against his former club since his move to Barca this summer.
Ousmane Dembele is sidelined with a hamstring injury, and the big question is whether Ivan Rakitic will keep his place after an impressive display on Wednesday.
Saturday also sees a Basque derby as Real Sociedad look to recover from last week's defeat against Real Madrid with a home game against Eibar, who are not looking like their usual compact selves this time around.
Real Mallorca entertain Real Betis in a game that could increase the pressure on Betis coach Rubi if his side lose, while there is an east coast derby at the Mestalla stadium as Valencia entertain Villarreal.
Villarreal need to bounce back after their home defeat to Celta a week ago, but Valencia will think that if they reproduce the football they showed in their 1-1 draw against Chelsea on Wednesday then the points will stay at home.
Third-placed Sevilla are at home to bottom of the table Leganes on Sunday, and Julen Lopetegui's side could theoretically go top if results elsewhere go their way.
Athletic Bilbao will look to build on last weekend's first away win of the season when they entertain Granada at 2 p.m. in the San Mames Stadium.
Raul Garcia is a doubt for Athletic, while Granada will be missing their central defender German Sanchez.
Second from bottom Espanyol desperately need all three points at home to an Osasuna side still smarting after last weekend's defeat to Athletic, while there looks to be an even game between Getafe and Levante, with the visitors hoping to take advantage of possible heavy legs following Getafe's Europa League tie in Turkey on Thursday night.
( With inputs from IANS )