These two nations only qualified for the competition in Germany through the playoffs and will now hope to generate some momentum ahead of bidding to try to reach the last 16.
Match preview
At a time when other nations have been looking to complete their friendlies with plenty of time in hand before Euro 2024, Poland have taken a different approach.
Even with their first game against Netherlands taking place on June 16, Poland are only starting their double-header of preparation games on Friday.
Head coach Michal Probierz may have prioritised an extra rest period before jumping into a hectic schedule, while Poland also have momentum from a six-game unbeaten streak.
Back in March, the Eagles thrashed Estonia by a 5-1 scoreline in their playoff semi-final, setting up a showdown with Wales where they were second-best and failed to land shots on target with any regularity.
However, Probierz's side scored each of their five penalties to win the shootout 5-4, securing a fourth-successive appearance at the European Championship.
Ukraine followed the same route as Poland to Euro 2024, launching comebacks against Bosnia-Herzegovina and Iceland to prevail 2-1 in each playoff tie.
Sergiy Rebrov's side have since continued their promising form with a goalless draw against Germany on Monday, making it just one defeat in 11 matches.
The Blue and Yellow are not necessarily expected to go deep into the competition, yet they have put themselves into a position where they are justified dark horses to upset some of the bigger nations.
Nevertheless, Ukraine have succumbed to defeat on the last two occasions that they have faced Poland, one of which coming at Euro 2016.
Just one friendly has been staged since then, though, with Poland winning 2-0 in Chorzow at the back end of 2020.
Poland form (all competitions):
W
D
D
W
W
W
Ukraine form (all competitions):
W
W
D
W
W
D
Team News
With Poland having all 11 players available from the starting lineup against Wales, Probierz may decide to stick with that team.
However, with a second game against Turkey to come on Monday, rotation remains possible with Sebastian Walukiewicz potentially replacing Jan Bednarek whose season with Southampton lasted longer than most.
Sebastian Szymanski is an option in midfield, while Jakub Kaluzinski and Kacper Urbanski will hope to make their debuts off the substitutes' bench.
Rebrov will almost certainly make several changes after the Germany draw with Artem Dovbyk in line to feature down the middle of the Ukraine attack.
Sergiy Sydorchuk, Georgiy Sudakov, Ruslan Malinovskyi and Andriy Yarmolenko are also in contention to be recalled.
Poland possible starting lineup:
Szczesny; Kiwior, Walukiewicz, Dawidowicz; Frankowski, Szymanski, Zielinski, Slisz, Zalewski; Swiderski, Lewandowski
Ukraine possible starting lineup:
Trubin; Konoplya, Zabarnyi, Matvienko, Svatok, Zinchenko; Tsygankov, Sydorchuk, Malinovskyi, Yarmolenko; Dovbyk
We say: Poland 1-1 Ukraine
Although Ukraine may have benefitted from their outing on Monday, Poland will feel fresher and better prepared. All things considered, these two well-matched teams may cancel each other out in a low-scoring draw in Warsaw.