Former Barca captain Luis Enrique will take charge of his first competitive game after replacing Gerardo Martino in the dugout, but many of the new faces in the playing staff are unlikely to feature.
Marc-Andre ter Stegen and Thomas Vermaelen are both sidelined by injury, while Luis Suarez continues his four-month ban for biting Italian defender Giorgio Chiellini during the World Cup.
Claudio Bravo and Ivan Rakitic are expected to make their competitive debuts, however, while Lionel Messi and Neymar will feature after both scored on their return from World Cup duty in Barca's 6-0 thrashing of Mexican side Club Leon on Monday.
Barca also lost the experience of goalkeeper Victor Valdes and Carles Puyol over the close season, but another veteran, right-back Dani Alves, believes he can see similarities in Luis Enrique's early days in charge to those of Pep Guardiola which reaped such success.
"It is a pleasure to work with someone like Luis Enrique, he demands a lot from us and in the end that is what makes us excited," Alves said yesterday.
"We are working well and demanding a lot of ourselves. The target this year is a marvellous one.
"I think the teams that want to keep winning titles always have to be in evolution. We have the principal thing, which is clear ideas that are accepted by everyone. All that we need to do now is execute them."
Elche provided a major stumbling block between Barcelona and the Liga title last season as they held Martino's men 0-0 at their own Martinez Valero Stadium in the penultimate game of the campaign.
And defender David Lomban believes his side can take heart from that result to the Camp Nou.
"There is never a good time to face Barcelona, but it also wasn't a good time towards the end of last season and we managed to get a draw," he said.
Champions League finalists Atletico Madrid and Real Madrid don't get their league campaigns underway until Monday night as they face off in the second leg of the Spanish Super Cup today.
La Liga champions Atletico have a tricky start as they travel across Madrid to take on a Rayo Vallecano side that produced a stunning late run last season to secure their survival in the top flight for another year.
Real, meanwhile, will also be looking to make amends as they crumbled in the final weeks of the league season in May before going on to claim a tenth European Cup by beating Atletico in Lisbon. They begin their league campaign at home to newly-promoted Cordoba.
There will be an early indication of Sevilla and Valencia's chances of competing for Champions League football when the two most improved squads outside the big three face off at the Sanchez Pizjuan tomorrow.
Europa League winners Sevilla have compensated for the loss of captain Rakitic with the arrivals of Gerard Deulofeu on loan from Barca, Argentine international Ever Banega and Iago Aspas from Liverpool amongst others.
Meanwhile, Valencia's immediate financial troubles have been eased as Singaporean entrepreneur Peter Lim has taken charge and revitalised the squad.
German World Cup-winner Shkodran Mustafi has replaced Barcelona-bound Jeremy Mathieu at the heart of the defence, Manchester City's newest midfield signing Bruno Zuculini has joined on loan for a year and prolific Spanish under-21 international Rodrigo has bolstered new coach Nuno Espirito Santo's attacking options.