La Blaugrana took third place in the 2020-21 La Liga season to secure another safe passage into the group stages, while Bayern's perennial reign of dominance in the German top flight continued.
Match preview
Having retained the faith of Joan Laporta and the rest of the powers-that-be at Barcelona for at least another year, Ronald Koeman has overseen a largely positive start to the 2021-22 season, with his side claiming seven points from their first three La Liga clashes.
Just before the international break, Barcelona sought to make it back-to-back home wins in the top flight during the visit of Getafe, where goals from Sergi Roberto and Memphis Depay either side of Sandro Ramirez's equaliser would propel La Blaugrana to a narrow, but potentially pivotal 2-1 success.
Barcelona were due to lock horns with fellow Champions League outfit Sevilla following the end of September's World Cup qualifiers, but with both teams impacted by the late arrivals of their South American contingents, the fixture has been postponed to a later date as Koeman seeks to improve his side's fortunes in Europe.
Not one Barcelona fan needs reminding how Paris Saint-Germain dispatched them 5-2 on aggregate in the round of 16 last term before prising Lionel Messi from their grasp, and with their final group-stage encounter of last season ending in a 3-0 loss to Juventus, Barca head into Tuesday's game winless in three Champions League matches.
However, the Catalan giants have not gone four games without a win in the Champions League since 2013 - with that run including their 7-0 aggregate defeat to Bayern in the semi-finals - and the German powerhouses also have fond memories of another recent Camp Nou drubbing.
Bayern's continental crown slipped off their head last term as they also fell victim to PSG in the 2020-21 tournament, but Julian Nagelsmann's side firmly have the look of a team itching to regain the coveted trophy this time around.
If the German champions had not laid down a marker by putting 12 unanswered goals past Bremer SV in the DFB-Pokal, they sure did by marching to a romping 4-1 success over RB Leipzig in league action at the weekend, with Robert Lewandowski, Jamal Musiala, Leroy Sane and Eric Maxim Choupo-Moting all scoring against Nagelsmann's former club.
Bayern prepare to travel to Camp Nou having won their last five games on the spin in all competitions - although they currently trail perfect Wolfsburg by two points in the Bundesliga standings - while their unbeaten away record in the Champions League is truly something to behold.
Indeed, Bayern have not suffered defeat on the road in Europe's elite tournament since losing 3-0 at PSG in September 2017 - winning 14 and drawing four away from home since then - which represents the longest-ever unbeaten streak away from home in the Champions League.
It is hard to believe that Bayern's infamous 8-2 drubbing of Barca was 11 months ago now, and the teams have not met in the group stages since the 1998-99 campaign, where the Bavarian giants claimed a pair of 1-0 and 2-1 victories.
Barcelona form (all competitions):
Bayern Munich form (all competitions):
Team News
Barcelona's attacking forces have taken quite the hit in recent weeks, with Antoine Griezmann returning to Atletico Madrid while Sergio Aguero (calf), Ousmane Dembele (hamstring) and Ansu Fati (knee) remain in the treatment room.
There are also doubts over Martin Braithwaite's availability after he was restricted to individual training on Saturday, so Depay and Philippe Coutinho may start either side of Luuk de Jong up top.
Jordi Alba has a strong chance of overcoming a knock in time to take his place on the left, but Sergino Dest is more uncertain, so Oscar Mingueza or Sergi Roberto will hope to get the nod at right-back.
Meanwhile, Bayern are relatively well-stocked for this mouthwatering affair, with French duo Kingsley Coman and Corentin Tolisso their only two absentees from the win over Leipzig with calf issues.
Serge Gnabry had to be withdrawn just before half time at the weekend, although Nagelsmann affirmed that the substitution was precautionary and is hopeful that the ex-Arsenal man will be passed fit here.
Marcel Sabitzer made his Bayern debut off the bench against his former employers Leipzig but has his work cut out to displace Leon Goretzka, Joshua Kimmich or Thomas Muller, the latter of whom boasts six goals in five games against Barca.
Barcelona possible starting lineup:
Ter Stegen; Roberto, Araujo, Pique, Alba; Busquets, F. de Jong, Pedri; Depay, L. de Jong, Coutinho
Bayern Munich possible starting lineup:
Neuer; Pavard, Upamecano, Hernandez, Davies; Kimmich, Goretzka; Sane, Muller, Musiala; Lewandowski
We say: Barcelona 0-2 Bayern Munich
While any Bavarian hopes of another six-goal thrashing may not be fulfilled, it is difficult to pinpoint any weaknesses in this Bayern side now that Lucas Hernandez and Benjamin Pavard have returned to bolster the rearguard.
Barcelona have started the season brightly under Koeman, but facing the side with the longest-ever unbeaten streak away from home in the Champions League surely only spells one outcome.