The Catalans won the corresponding fixture 6-0 in 2016-17, but lost 2-1 at home to the Basque outfit, whom they then beat 3-1 in the final of the Copa del Rey in May.
This match is the first on the road in La Liga for coach Ernesto Valverde, who started his playing career at Alaves.
Barca kicked off their league campaign on Sunday with a 2-0 win at home to Betis and here, Goal looks at everything you need to ahead of their second Primera Division game of the season...
Luis Suarez is sidelined for around four weeks after picking up a knee injury in the second leg of the Supercopa against Real Madrid at the Santiago Bernabeu last week.
However, Andres Iniesta is set to return after missing both the game against Madrid and Barca's Liga opener last week versus Betis, while Gerard Pique is also fully fit after picking up a knock at the Bernabeu and staying on the bench for the 90 minutes last Sunday.
Jordi Alba was the only Barcelona player to be booked in the win over Betis and coach Ernesto Valverde does not have any players suspended for the game against Alaves.
BARCELONA POTENTIAL STARTING LINE-UP
Barcelona played with a 4-2-3-1 formation in the 2-0 win over Betis last Sunday and that is coach Ernesto Valverde's preferred formation.
With Luis Suarez sidelined, Lionel Messi will start in attack, while Andres Iniesta is available again after injury and could return to the side on the left of the three behind the Argentine attacker.
Iniesta is unlikely to feature for 90 minutes, however, and may be on the bench at Mendizorrotza, where Denis Suarez and Andre Gomes are also in contention for starting spots.
Gerard Pique will return in defence after making a full recovery from the injury which saw him left out against Betis.
Meanwhile, new signing Ousmane Dembele is not eligible to make his debut on Saturday and will have to wait until next weekend's derby against Espanyol.
ALAVES TEAM NEWS
Alaves impressed in La Liga last season, finishing ninth in the Primera Division and also reaching the final of the Copa del Rey, losing 3-1 to Barcelona at the Vicente Calderon.
However, two of the Basques' best performers from the 2016-17 campaign were on loan and are now both at Real Madrid, Theo Hernandez signing for Los Blancos from Atletico and Marcos Llorente returning to his parent club for the new season.
"Barca have a great team, even if they are missing players," defender Rodrigo Ely said this week in reference to the sale of Neymar and the injury to Suarez.
Alaves have no injury concerns ahead of the game against the Blaugrana.
BEST OPTA MATCH FACTS
Alaves have only won one of their last seven games against Barcelona in La Liga (losing four and drawing two), a 2-1 at Camp Nou last season.
In the corresponding fixture in 2016-17, Barca won 6-0 and that was the biggest league loss ever for Alaves at Mendizorrotza.
Barcelona have won their last eight games in La Liga, their longest winning run in the competition.
Lionel Messi has scored 349 goals in La Liga, and could become the second player from the top five European leagues to reach 350 goals for the same club, after Gerd Muller with Bayern Munich (365 in total).
TV COVERAGE & KICK-OFF TIME
Alaves versus Barcelona kicks off at 18:15 local time on Saturday and will be shown live in the UK on Sky Sports mix from 17:10 BST.