Poland have won all three of their matches so far, beating Portugal, Israel and North Macedonia 3-0.
Ukraine have played four matches, beating Israel 3-1 and North Macedonia and Portugal 3-0 before producing an upset 3-1 victory over Bulgaria, the reigning world runners-up.
The result secured Ukraine's place in the knockout stage.
A victory over Poland on Tuesday would put Ukraine in a strong position to finish top of Group B and secure a favourable path through the knockout stage.
Poland, however, will enter the match as favourites.
Coach Nikola Grbić's team is the world's top-ranked side and defending European champions.
Poland most recently faced Ukraine in the quarterfinals of this year's Volleyball Nations League, winning 3-1.
Several days later, Poland won the Nations League title for the second consecutive year.
The match is scheduled to start at 6 p.m. Warsaw time.
The European championship is co-hosted by Finland, Romania, Bulgaria and Italy.
Poland are playing their group-stage and knockout matches through the quarterfinals in Sofia, while the semifinals and final will be held in Milan.
(gs)
Source: IAR/PAP