The match will see former Barcelona midfielder Mark van Bommel return to the Camp Nou with his PSV side who have begun the defence of their title with five straight wins and 21 goals scored.
PSV are seen as the weakest team in the group, but it’s worth noting they warmed up for the match with a 7-0 thrashing of ADO Den Haag.
Here’s a look at how Barcelona may line up for the match:
The only real debate at the back concerns the right-back position. Given Nelson Semedo was substituted at half-time on Saturday it seems certain Sergi Roberto will start there.
Clement Lenglet is the only other real contender for a place. The Frenchman is still waiting for his first Barcelona start, but he may just have to wait a little longer.
Expect Gerard Pique to partner Samuel Umtiti at the heart of the defence, Jordi Alba to feature at left-back and Marc-Andre ter Stegen to continue in goal.
Ernesto Valverde experimented with his midfield against Real Socieded but don’t expect any more rotation against PSV.
Sergio Busquets and Philippe Coutinho were left out of the starting line-up at Anoeta, but they should come back in alongside Ivan Rakitic.
Valverde has loads of options in midfield this season, but he’s expected to go with his strongest XI with Barca’s focus very much on the Champions League this season.
Ousmane Dembele is starting to cement his place in the starting XI and will surely start after scoring his third La Liga goal of the season on Saturday.
Luis Suarez was also on target, as he appears to have shaken off his early season sluggishness. Can he now shake off his poor goalscoring form in the Champions League?
And then there’s Lionel Messi. Valverde surprisingly left him on the bench for the group game against Juventus last season, but the captain should lead the team out on Tuesday.
Probable starting XI: Ter Stegen; Robert, Pique, Umtiti, Alba; Rakitic, Busquets, Coutinho; Messi, Suarez, Dembele.
How do you think Barcelona should line up against PSV? Let us know your line-ups, score predictions and thoughts in the comments below!