The game kicks off at 6 p.m. in the southwestern Polish city of Wrocław.
Poland, captained by star striker Robert Lewandowski, are looking to put up a strong performance as they start a series of matches against high-ranked European teams in the run-up to this year's World Cup in Qatar.
Poland are ranked 26th worldwide by football's governing body FIFA, while Wales are No. 18 in the FIFA table.
At a pre-match news conference in Wrocław on Tuesday, Poland manager Czesław Michniewicz said: "We will field our best line-up; we will try and give everyone who is in good shape a game. We will play four at the back, but we will change the line-up."
Poland boss Czesław Michniewicz. Photo: PAP/Maciej Kulczyński
Poland will take on Belgium in Brussels on June 8 and the Netherlands in Rotterdam on June 11 in their next Nations League fixtures.
On June 14, Poland will face off against Belgium on home turf in Warsaw.
The Nations League is the European football governing body UEFA’s newest national-team competition that is now in its third edition.
The competition is designed to enable teams to play against those that are similarly ranked and may also offer an alternative path for teams to qualify for the 2024 European championships.
Portugal won the first edition of the Nations League in 2019, while France won the 2020/2021 UEFA Nations League after beating Spain 2-1 in the final in Milan in October.
The 2022 World Cup, meanwhile, will be held in Qatar from November 21 to December 18.
Poland have been drawn to play Argentina, Mexico and Saudi Arabia in the group stage of the tournament.
The Polish team qualified for the World Cup after defeating Sweden 2-0 in a playoff at home in late March.
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Source: PAP, uefa.com