Xavi's first full season in charge of Barcelona begins at the Nou Camp against Rayo Vallecano, while Diego Simeone's Atletico Madrid kicks off its campaign away from home against Getafe.
Elsewhere on the opening matchday, Sevilla travel to Osasuna, Athletic Bilbao host Mallorca and play-off winners Girona face Valencia.
The LaLiga season begins on 12 August and will run until a mid-season break for the World Cup in Qatar, with the campaign pausing on 13 November and resuming on 29 December.
LaLiga Round 1 fixtures:
Athletic Club v RCD Mallorca
FC Barcelona v Rayo Vallecano
Real Betis v Elche CF
RC Celta v RCD Espanyol de Barcelona
Cádiz CF v Real Sociedad
CA Osasuna v Sevilla FC
UD Almería v Real Madrid
Getafe CF v Atlético de Madrid
Real Valladolid CF v Villarreal CF
Valencia CF v Girona FC