The game starts at 8:45 p.m. at the National Stadium in the Polish capital.
Poland are ranked 28th worldwide by football's governing body FIFA, while Ukraine are No. 22 in the FIFA table.
At the end of last month, Poland boss Michał Probierz released an initial list of 29 players called up for the upcoming European championships in Germany.
The lineup announced by Probierz includes star striker Robert Lewandowski and other regulars such as Napoli midfielder Piotr Zieliński and Juventus goalkeeper Wojciech Szczęsny.
Poland, captained by Lewandowski, in March earned a berth in the European championships after defeating Wales 5-4 on penalties in a playoff in Cardiff.
The Euro 2024 tournament will be held from June 14 to July 14 in 10 cities in Germany, with the final played at Berlin's Olympiastadion.
The Poles will face France, the Netherlands and Austria in the group stage of the tournament, following a draw in Germany in December.
The Polish team will open its Euro group-stage campaign with a fixture against the Netherlands in Hamburg on June 16.
The Poles will next take on Austria in Berlin five days later and then play France in Dortmund on June 25.
Ahead of the European tournament, Poland will also play a friendly against Turkey at the National Stadium in Warsaw on June 10.
The Polish Football Association (PZPN) in April announced that Hanover in northern Germany would be the official training base for the national squad during Euro 2024.
Poland failed to get past the group stage at the postponed Euro 2020 tournament, where they suffered a defeat to Slovakia before drawing with Spain and losing the decisive game against Sweden.
The Polish team made it through to the quarterfinals of the Euro 2016 championships in France, losing to Portugal on penalties.
Poland reached the last 16 of the 2022 World Cup in Qatar before being eliminated by eventual runners-up France.
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Source: IAR, PAP
Ahead of the game, Radio Poland's Danuta Isler interviewed Oleksandr Hlyvynskyy, press officer for the Ukrainian Football Association.
"Both teams qualified for Euro 2024 through playoffs, so that is important, but I also think it will be a real friendly match because we appreciate Poland's support from the beginning of the full-scale Russian invasion of Ukraine," Hlyvynskyy said.
"I think it will be a good preparation for both teams," he added.
Oleksandr Hlyvynskyy. Photo: Danuta Isler/Radio Poland
Click on the audio player above to listen to the interview.