The hosts have the chance to move off the bottom of the table if they can claim a victory.
Match preview
After securing back-to-back promotions to rise from League D to League B, Armenia are at risk of being relegated back to the Nations League's third tier at the end of the current campaign.
Despite beating Republic of Ireland 1-0 at the Vazgen Sargsyan Republican Stadium in their opening match, three successive defeats have left them bottom of Group E, one point behind Ireland.
However, given that they face Ireland away from home on Tuesday, Saturday's match against Ukraine in Yerevan takes on additional significance; a win would keep their destiny in their own hands heading to Dublin next week, providing Scotland do not lose to Stephen Kenny's side at the weekend.
Having never reached a major tournament as an independent nation, avoiding relegation would help ensure that their FIFA World Ranking does not slip further, with their seeding potentially suffering as a result.
Indeed, after reaching an all-time high of 30th in February 2014, the Mountaineers have fallen to 92nd in the world in recent times, despite former Sevilla boss Joaquin Caparros making a decent enough impact since being appointed in March 2020.
Ukraine, meanwhile, were overtaken in top spot by Scotland in Group E after Steve Clarke's side ran out 3-0 winners at Hampden Park on Wednesday.
The hosts looked the more threatening side throughout, with Oleksandr Petrakov's mustering just three shots throughout the course of the match, compared to Scotland's tally of 24, with eight of those testing goalkeeper Anatoliy Trubin.
Aston Villa's John McGinn finally broke the deadlock after 70 minutes, before substitute Lyndon Dykes bagged a quickfire brace to ensure the Scots gained revenge after Ukraine's 3-1 win against them in June in a one-legged World Cup qualifying play-off.
The two sides meet again in Krakow next Tuesday, but if Petrakov's side are to have promotion to League A in their control heading into that reverse fixture, they must beat Armenia on Saturday and hope for a favour from Ireland.
Armenia Nations League form:
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Armenia form (all competitions):
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Ukraine Nations League form:
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Ukraine form (all competitions):
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Team News
Armenia will be without Varazdat Haroyan and Eduard Spertsyan due to suspension, with the duo accumulating one yellow card too many in their nation's 4-1 defeat to Scotland in June.
Arman Hovhannisyan and Kamo Hovhannisyan were both sent off in that match, but neither have been included in Caparros's squad for the upcoming fixtures.
Sergey Mkrtchyan and Serob Galstyan will hope to make their international debuts at some point across the next week.
Ukraine, meanwhile, could replace Artem Dovbyk with Roman Yaremchuk in attack as Petrakov looks to increase his side's goal threat after a poor showing in the defeat to Scotland on Wednesday.
Given that his side have three fixtures in the space of seven days, further rotation is likely to occur ahead of the reverse fixture against the Scots on Tuesday, with Vitaliy Mykolenko, Serhiy Sydorchuk and Oleksandr Zubkov being the likeliest contenders to come into the starting XI.
Oleksandr Zinchenko was not named in his country's squad due to a calf injury, which kept him out of Arsenal's victory over Brentford last weekend.
Armenia possible starting lineup:
Yurchenko; Dashyan, Hambardzumyan, Voskanyan, Mkoyan, Hakobyan; Grigoryan, Babayan, Bayramyan; Zelarayan, Barseghyan
Ukraine possible starting lineup:
Trubin; Karavayev, Bondar, Matviyenko, Mykolenko; Zubkov, Sydorchuk, Malinovskyi; Yarmolenko, Yaremchuk, Mudryk
We say: Armenia 1-3 Ukraine
With Ukraine missing two of their most experienced and talented players through suspension, we can envisage a comfortable victory for the visitors.
They are likely to enjoy playing with more freedom and attacking verve than when being held at arm's length by Scotland in midweek, with victory on Saturday keeping their hopes of promotion to the Nation League's top tier alive ahead of next week's reverse fixture.