The 2013 winners have had a mixed start to their Bundesliga campaign, taking eight points from four games, while Belgrade, who have already beaten four teams to reach the group stage, have won six from six domestically.
Niko Kovac's side start this Champions League determined to improve on last season's showing, which saw them eliminated in the last 16 by eventual winners Liverpool.
Encouragingly, the Bavarian giants boast an excellent recent record in the group stage of this competition, scoring in 28 consecutive games at the Allianz Arena.
Although Bayern have only won twice in the Bundesliga thus far this season, they have been highly effective going forward, with summer signings Benjamin Pavard and Ivan Perisic contributing to their tally of 15 goals in six competitive matches.
Polish striker Robert Lewandowski is already up to seven goals for the season and his ability to link play will be essential against a side like Red Star, who will be content to sit back for long periods.
Wednesday's game will be the first between the two sides since October 2007, when Bayern won 3-2 in a UEFA Cup group stage game.
For Red Star, this will be their second successive season in the Champions League after making their debut last year, when they shocked many by beating Liverpool before eventually finishing bottom of their group.
To reach the group stages this year, Vladan Milojevic's side have already recorded aggregate triumphs over FK Suduva, HJK Helsinki, FC Copenhagen and Young Boys.
Key to last season's famous win was striker Milan Pavkov, who scored a double and the forward fired in another brace at the weekend against Indija to take him to six goals in eight games for the season.
Central to Red Star's hopes of victory will be centre-back Milos Degenek, the team's main defensive organiser, captain Marko Marin, their main playmaker, and wingers Aleksa Vukanovic and Ben Nabouhane, their key avenues of attack on the counter.
Bayern Munich recent form (all competitions): LWDWWD
Red Star Belgrade recent form (all competitions): DWDDWW
Alaba got injured in the warm-up before the Leipzig game, while Goretzka recently underwent surgery to correct a thigh problem.
Red Star will be without the services of Portuguese striker Tomane, as he is suspended following his red against Young Boys in the last round, but beyond that Milojevic could stick with the side that won on Saturday.
Bayern Munich possible starting lineup:
Neuer; Pavard, Sule, Boateng, Hernandez; Kimmich, Thiago; Coman, Coutinho, Gnabry; Lewandowski
Red Star Belgrade possible starting lineup:
Borjan; Gobeljic, Degenek, Babic, Rodic; Canas, Jovancic; Nabouhane, Marin, Vukanovic; Pavkov.
We say: Bayern Munich 4-1 Red Star Belgrade
Bayern simply have too much quality across the field, especially in the attacking areas, for their Serbian opponents but it wouldn't be a shock to see the away side cause them a few issues along the way.