Klaudia Jedlińska opened the scoring in the 18th minute and Paulina Tomasiak doubled the lead in the 64th.
Kayla Adamek made it 3-0 four minutes into stoppage time, and Milena Kokosz sealed the win with a goal in the 96th minute, Polish state news agency PAP reported.
With the victory in the southeastern Polish city of Mielec, Poland extended their unbeaten streak to 11 matches, including four wins last year and six wins and a draw so far this year.
Poland are ranked 27th worldwide by football's governing body FIFA, while Ukraine are No. 35 in the FIFA table.
Earlier this month, Poland coach Nina Patalon named the final 23-player squad for next month’s European championships in Switzerland.
The lineup announced by Patalon includes Barcelona Femeni striker Ewa Pajor, who recently earned her 100th cap for the national team.
She did not play against Ukraine on Friday.
Women's Euro 2025, which will feature 16 teams, marks Poland’s first-ever appearance in the continental championships.
"This is a special moment for the team," Patalon said. "We will do our best to prepare for the tournament as best as we can."
Poland are scheduled to fly to Switzerland on Monday.
The Euro 2025 tournament runs from July 2 to 27.
Poland have been drawn into a group with Germany, Sweden and Denmark, and will open their campaign against Germany on July 4.
In early June, more than 10,000 fans attended the Polish team's 3-0 home victory over Romania in the UEFA Nations League, setting what officials said was a record for women’s football attendance in Poland.
(gs)
Source: IAR, PAP, pzpn.pl