Barcelona and Real Madrid both face matches against tough Spanish league rivals on Sunday after a pair of lacklustre performances.
Barcelona visit Valencia after winning the Spanish Super Cup on Wednesday despite being outplayed by Atletico Madrid in a 0-0 home draw in which Lionel Messi missed a late penalty.
Madrid have pulled out two uninspiring wins by a one-goal margin to start the season and host an Athletic Bilbao side that has also proved perfect through the opening two rounds.
Also, Real Sociedad host Atletico Madrid in a meeting of Spain's other two Champions League sides.
Friday 30 August
Almeria v Elche
Rayo Vallecano v Levante
Saturday 31 August
Celta de Vigo v Granada
Valladolid v Getafe
Osasuna v Villarreal
Sunday 1 September
Real Madrid v Athletic Bilbao
Espanyol v Real Betis
Real Sociedad v Atl Madrid
Sevilla v Malaga
Valencia v Barcelona
Barcelona started the season with a 7-0 thrashing of Levante. But since then they have had a 1-0 win at Malaga and two draws with Atletico that have raised doubts about their form under new coach Gerardo Martino.
Not even new signing Neymar playing all 90 minutes could help Barcelona break through Atletico's disciplined defence Wednesday.
"We have to improve the circulation of the ball, be faster, try to find more spaces so we can score,'' Barcelona defender Gerard Pique said.
"We will do it. Our attitude is good. Against Valencia we have to show our best version to take the three points.''
Questions of Messi's fitness have yet to go away either. The Argentina forward has already sustained two minor muscle injuries in recent weeks after missing several games at the end of last season due to a hamstring pull.
Messi played the entire game against Atletico, but was lacking his usual spark and deadly finishing touch.
Valencia coach Miroslav Djukic scolded his players after last week's bad loss at Espanyol. It will be interesting to see if they respond with an energised effort at home on Sunday or if this is the beginning of a split between the squad and staff.
Valencia bolstered their humdrum attack by signing striker Dorlan Pabon this week.
Madrid host Bilbao amid two ongoing sagas that are coming to a head.
For several days, Madrid have been expected to complete a blockbuster deal with Tottenham to secure the transfer of Wales forward Gareth Bale. The transfer window closes on Monday night.
The other major distraction is Madrid coach Carlo Ancelotti's decision to keep Diego Lopez as a starter and Spain captain Iker Casillas as the team's backup. That move was first made by former coach Jose Mourinho last season and has been a target for criticism by Madrid fans and the Spanish media ever since.
Bilbao manager Ernesto Valverde has helped the Basque team tighten up their defence from last season when under Marcelo Bielsa it was shredded again and again by rivals.
They will have to keep Cristiano Ronaldo in check with the Portugal forward eager to score his first Madrid goal of the campaign.
Sociedad earned a spot in the group stage of the Champions League by beating Lyon 2-0 Wednesday to eliminate the French side 4-0 on aggregate.
Carlos Vela scored both goals for Sociedad in the second leg, giving the forward four goals in as many games this season.
Atletico are playing the best football in Spain right now with two lopsided wins in the league and two more-than-dignified draws against Barcelona in the Super Cup.
"The team has grown a lot,'' said coach Diego Simeone, who guided Atletico to the Copa del Rey title and a third-place finish in the league last season.
"There is an enormous sense of commitment by the players, which is what this team needs.''
Also on Sunday, Real Betis visit Espanyol and Sevilla host Malaga with both Seville-based clubs seeking their first victory.
On Saturday, Villarreal will be aiming for a third straight win at Osasuna, Valladolid host Getafe, and Granada plays at Celta Vigo. On Friday, Elche visit Almeria in a meeting of two promoted sides, while Levante are at Rayo Vallecano.