Celta Vigo vs. Atletico (Sunday, 4.30pm)
Los Colchoneros pipped city rivals Real Madrid to the trophy last campaign, while their hosts eventually finished in eighth spot after a mixed season.
We say: Celta Vigo 0-2 Atletico Madrid
Despite facing a tough test to start the season, we can only envisage Simeone's side beginning with a victory on Sunday.
Given the situations at Real Madrid and Barcelona, Atletico Madrid have reason to be confident that they can retain the title this year, and a winning start for Los Colchoneros will be crucial to help build a positive run and establish themselves at the top end of the division.
Barcelona vs. Real Sociedad (Sunday, 7.00pm)
Barcelona will be looking to make the perfect start to their 2021-22 La Liga campaign when they welcome Real Sociedad to Camp Nou on Sunday night.
Ronald Koeman's side finished third in Spain's top flight last term, seven points behind champions Atletico Madrid, while Real Sociedad claimed fifth to secure a spot in the Europa League group stages.
We say: Barcelona 1-1 Real Sociedad
Real Sociedad are very dangerous opponents for Barcelona on the opening weekend, and we would not be too surprised to see an away win on Sunday night. That said, there is still plenty of quality in the home side's ranks, and we are expecting the two teams to play out a draw at Camp Nou.
Sevilla vs. Rayo Vallecano (Sunday, 9.15pm)
Sunday's hosts achieved a top-four finish for the second straight campaign last season, earning Champions League football, while their visitors made a return to the top flight after winning the Segunda Division playoffs last year.
We say: Sevilla 2-0 Rayo Vallecano
Given their superior squad, Sevilla should brush the newly-promoted outfit aside on Sunday.
Lopetegui's men will have their sights set on the top four again this season, and a winning start will be important, especially with a tough schedule coming up.