Though the troubled nation's World Cup dreams are over, they are tied on points with their visitors and Scotland at the top of the early League B Group 1 table, and will now host a first match at their new adopted home.
Match preview
After enduring the pain of losing out to Wales in the World Cup playoffs last Sunday, perhaps wisely, Ukraine coach Oleksandr Petrakov decided to rotate his squad for a midweek trip to Dublin.
With a radically overhauled starting XI, featuring several young stars, the Blue and Yellow saw substitute Viktor Tsygankov's rather fortuitous strike seal all three points against the Republic of Ireland; kicking off their latest Nations League campaign in successful style.
The Dynamo Kyiv winger's in-swinging free kick eluded Irish goalkeeper Caoimhin Kelleher just after the interval, and puts Ukraine on the road to regaining League A status next year.
Controversially demoted from the top tier in 2020, after a COVID-19 outbreak forced former coach Andriy Shevchenko's squad to pull out of a fixture with Switzerland - with the points later being allocated to the Swiss - the intent to right a perceived injustice will be strong.
Most of the Ukraine squad have been starved of regular football over recent months, due to the national league being suspended since Russia's invasion, but wins against Scotland and Ireland in their last three competitive games - and such a close call against Wales - have demonstrated the talents of a squad that reached the Euro 2020 quarter-finals.
Days after recording one of their most notable wins in years by defeating the so-far pointless Irish, another Celtic challenge awaited Armenia on Wednesday, when they took on Scotland at Hampden Park.
Their first away fixture of the new Nations League campaign ended in defeat, however, after conceding two first-half goals against Steve Clarke's side, who had suffered playoff elimination to Ukraine in their previous outing.
Nonetheless, three points from Armenia's first two matches at League B level represents success for head coach Joaquin Caparros, a wily veteran who was present at the start of Sevilla's rise to prominence as a force in Europe.
The 66-year-old was also in charge as Armenia secured promotion from League C at the end of 2020, when they finished ahead of Estonia, Georgia and North Macedonia in their group.
With a first competitive win since beating Romania in World Cup qualifying last year already in the bag, a side thumped 9-0 by Norway in March will now look to overcome their setback in Glasgow, as they tackle the Group 1 favourites on Saturday.
Ukraine Nations League form:
Ukraine form (all competitions):
Armenia Nations League form:
Armenia form (all competitions):
Team News
Facing the fourth of five competitive games to be played in quick succession, Oleksandr Petrakov is poised to shake up his starting XI again, after making 10 changes on Wednesday.
Viktor Tsygankov could be rewarded for a positive showing and scoring the winner against Ireland with selection out wide, while Eduard Sobol may return at left-back as Everton's Vitaliy Mykolenko takes a rest.
Up front, meanwhile, Roman Yaremchuk is likely to be drafted back in for Artem Dovbyk, with captain and leading active goalscorer Andriy Yarmolenko (108 caps, 45 goals) also coming back into contention. However, young Mykhaylo Mudryk could hold down his spot due to some eye-catching displays so far this summer.
Armenia, though, have a shallower pool of creative players to draw from - particularly since Henrikh Mkhitaryan's international retirement last year - and are likely to field a similar side to that which lost at Hampden.
Colombus Crew striker Lucas Zelarayan and back-up defender Hayk Ishkhanyan are set to miss out due to injury, so Sargis Adamyan should start in the absence of the former up front, while Colombia-born pair Jordy Monroy and Wbeymar Angulo are among several men hoping for promotion from the bench.
Ukraine possible starting lineup:
Lunin; Karavaev, Zabarnyi, Matvienko, Sobol; Shaparenko, Sydorchuk, Malinovskyi; Yarmolenko, Yaremchuk, Mudryk
Armenia possible starting lineup:
Yurchenko; Hambardzumyan, Haroyan, Mkoyan, Mkrtchyan, A. Hovhannisyan; Bayramyan, Grigoryan; Spertsyan, Barseghyan; Adamyan
We say: Ukraine 3-0 Armenia
Despite the backdrop of conflict at home, and the crushing disappointment of missing out on Qatar 2022, Ukraine have acquitted themselves admirably over the last fortnight, and they are comfortably at home in League B.
Armenia, meanwhile, are still new to this level of Nations League competition, and are not particularly prolific - drawing a blank in four of their last seven games. Their weekend trip to Poland, then, should end pointless.