While the home side will be playing their first match of this season's competition, Pyunik have already come through two ties to reach this stage.
Match preview
Having not lost a competitive fixture since their defeat in the first leg of their Europa League last-16 tie with Rangers in March, it is fair to say that Red Star are in a good place heading into this game.
The disappointment of that missed opportunity against the Scottish outfit will only add fuel to the fire ahead of this campaign, and there are high expectations regarding a return to the group stages for the first time since 2019.
Red Star have recently begun the defence of their top-flight crown in dominant fashion, prevailing in each of their opening four games and scoring 17 times in the process.
Although they are yet to face any of their title rivals, Dejan Stankovic's team are trending in the right direction significantly aided by their firepower in attack.
Long-serving forward Milan Pavkov has stood out thus far, the 28-year-old contributing five goals during the first quartet of matches.
After not winning any domestic silverware since 2015, it goes without saying that Pyunik are still riding a crest of a wave having won last season's Armenian title.
Expectations were naturally low with regards to going deep in qualifying, never mind challenging for a group-stage spot, but Yegishe Melikyan has overseen victories over CFR Cluj and F91 Dudelange.
In the first of those ties, Pyunik scored last-gasp goals in normal and extra time before winning on penalties in Romania, while they came from a 2-0 deficit on aggregate against Dudelange before netting four times in the away second leg to progress.
They are the clear underdogs for this tie - a feeling strengthened by losing the first game of their title defence at the weekend - but Melikyan's side will relish the opportunity to continuing to perform without any pressure on their shoulders.
Red Star Belgrade form (all competitions):
FC Pyunik Champions League form:
FC Pyunik form (all competitions):
Team News
With their last league fixture having taken place on Friday and ending in a 6-0 win, Stankovic may be prepared to stick with the same Red Star XI.
Pavkov came off the substitutes' bench to score against Radnik so is in contention for a recall, but Stankovic may be against tinkering with his side.
Operating with a 4-4-2 formation also looks most likely, rather than a back three that has also been used on occasions.
Luka Juricic is pushing for an opportunity in the Pyunik side after netting twice as a substitute in the second meeting with Dudelange.
Should that prove to be the case, Uros Nenadovic would drop out, while Eugeniu Cociuc is also an option in midfield after the impact that he made in central midfield in the same circumstances.
This game is likely to come too soon for the injured Sergiy Vakulenko, but the defender may be in a position to return for the second leg.
Red Star Belgrade possible starting lineup:
Borjan; Dragovic, Milunovic, Rodic, Gobeljic; Kangwa, Ivanic, Kanga, Mitrovic; Katai, Pesic
FC Pyunik possible starting lineup:
Yurchenko; Juninho, Gajic, Kovalenko; Davidyan, Mensalao, Zambrano, Harutyunyan, Dashyan; Juricic, Otubanjo
We say: Red Star Belgrade 3-1 FC Pyunik
With confidence high in the camp of the visitors, it would be naive to write them off in this tie. However, while we are backing Pyunik to get on the scoresheet in Belgrade, Red Star are the clear favourites and should head into the reverse fixture in control.