Last weekend's opening round in the top two divisions was postponed by a players' strike called by the Association of Spanish Footballers (AFE), who were in dispute with the Liga de Futbol Profesional (LFP) over unpaid wages.
The AFE wanted a guaranteed fund to protect players' wages in the event of their clubs being declared insolvent.
The initial strike action also included this coming weekend's fixtures, but following a week of talks between the AFE and LFP it was announced this afternoon that a resolution had been reached, meaning the second round of matches will take place as scheduled.
The highlight of those games takes place on Monday night when Barca host a Villarreal side that finished fourth last season.
Barca, who won both La Liga and the Champions League last term, have already added to their considerable trophy haul under coach Pep Guardiola with victory over arch rivals Real Madrid in the Spanish Supercopa last week, and they can pick up more silverware on Friday in the UEFA Super Cup against Porto.
Should Barca claim that crown then it would be the 12th major trophy they have won since Guardiola took charge in 2008.
It is an incredible period of success for the Catalan club, but Guardiola has dismissed any suggestion they are untouchable.
He said: "We are not invincible. Each team can beat us. If we receive praise it's because we play well and because we've won 11 titles, but in sport the most important thing is the following game and now we need to focus on that.
"We need to show that the players still have desire to have the best game possible."
Real Madrid begin their quest for a first La Liga title since 2008 with a trip to Real Zaragoza on Sunday.
Madrid coach Jose Mourinho has again found himself in the spotlight following his behaviour during the second leg of the Supercopa, where he appeared to put a finger in the eye of Barca assistant Tito Vilanova during a mass brawl at the end of the match.
The Spanish Football Federation announced on Tuesday that Mourinho, who will this season serve a UEFA-imposed touchline ban in Europe after comments made about Barca during similarly ill-tempered clashes between the two arch rivals in last season's Champions League semi-finals, was under investigation for his role in the incident.
The Portuguese has come under fire for his actions but Madrid defender Sergio Ramos insists the players are fully behind their coach.
"Mourinho has the full support of the squad. He leads this group of players, as such we're ready to do whatever he wants. He will always have our support, just like we have his," the Spain international said on his club's website following last night's 2-1 friendly victory over Galatasaray.
Elsewhere, there is an intriguing clash at the Ramon Sanchez Pizjuan where Sevilla host big-spending Andalusian rivals Malaga.
Malaga, whose week-one fixture would have pitted them against Barca, have brought in the likes of Santi Cazorla, Ruud van Nistelrooy, Joaquin and Jeremy Toulalan this summer.
Atletico Madrid have also splashed the cash following the summer departures of key players Sergio Aguero, David de Gea and Tomas Ujfalusi, including spending an initial 40million euros - rising to a possible 47million euros - on prolific Colombian Falcao.
Atletico being their campaign at home to Osasuna.
In other matches, Valencia meet Racing Santander, Real Mallorca host Espanyol, Levante go to Getafe and Sporting Gijon take on Real Sociedad. Top-flight newcomers Granada and Real Betis face each other, while the other promoted club, Rayo Vallecano, visit Athletic Bilbao.
Athletic Bilbao vs Rayo Vallecano
Getafe vs Levante
Barcelona vs Villarreal