La Blaugrana are expected to ease past their upcoming opponents, who aren't thought to stand a chance against Ernesto Valverde's side.
Alaves claimed a decent 14th-place finish in the Primera Division last season and finished 18 points above the relegation zone. However, they are tipped to be heavily involved in the relegation battle and couldn't have asked for a worse start to their season.
Despite the odds being heavily stacked against them, the Basque side won't be blamed for fancying their chances. They did beat Barca 2-1 in 2016 and are actually the last side to have beaten the champions at their Camp Nou home.
One of the best matches between these two sides took place during the 2001/2002 season, on April 14, 2002, at the Camp Nou. Back then, Barca boasted the likes of Phillip Cocu, Marc Overmars, Fabio Rochemback, Javier Saviola and Luis Enrique, who all started.
They also fielded a 22-year-old Xavi Hernandez and a 24-year-old Carles Puyol.
Alaves, meanwhile, started a former Barcelona midfielder in Jordi Cruyff, as well as Fabricio Collocini and Oscar Tellez.
Saviola opened the scoring for the home side in the 13th minute, with Xavi providing the assist. And the future Barca legend laid on another assist to hand his side a 2-0 lead in the 66th minute through Rochemback's strike.
Alaves hit back five minutes later, thanks to substitute Magno Moselin, and cut Barca's lead in half, but Xavi provided yet another assist, this time for Saviola, to give La Blaugrana a 3-1 lead in minute 88.
That should have been that, but the visitors kept coming and their efforts resulted in a stoppage-time goal from Daniel Alonso, whose 93rd-minute strike cut the deficit to just one. Unfortunately, time wouldn't permit any more goals in what turned out to be a real spectacle.
All eyes will be on Lionel Messi, Philippe Coutinho and Luis Suarez. New boys Arturo Vidal and Malcom, should they feature, will also command some attention. Yet this game could be won and lost deep in midfield.
Alaves will give themselves the best chance of emerging victorious if they cut the supply lines and stifle Sergio Busquets.
They do have tough midfielders such as Thomas Pina, Wakaso Mubarak and Manu Garcia, who could all bother the Spanish star, but skipper Garcia could be the one tasked with keeping him quiet.
The winner of this midfield battle could see his team come out on the winning end, yet Alaves still stand a huge chance of losing even if they succeed in stopping Busquets, given Messi's brilliance.
The home side have a nearly fit squad, with just Denis Suarez and Andre Gomes (both hamstring) out until next month. Carles Alena (hamstring) and Sergi Samper (knee) have both returned to training and could possibly feature if called upon, although that is unlikely.
Alaves, meanwhile, have five players injured at the moment. Fernando Pacheco (shoulder), Alfonso Pedraza (thigh) and Rodrigo Ely (cruciate ligament) will surely miss this one. But Hector Hernandez (knee) and Alexis (groin) have been training.
Barcelona: Ter Stegen, Semedo, Umtiti, Pique, Jordi Alba, Rakitic, Busquets, Vidal, Suarez, Messi, Coutinho.
Alaves: Pacheco, Marin, Aguirregabiria, Navarro, Laguardia, Pina, Sobrino, Garcia, Wakaso, Burgui, Guidetti.