Poland opened its campaign last week, beating Wales 2-1 in Wrocław, following goals from Jakub Kamiński and Karol Świderski.
Belgium, meanwhile, lost their opening game 4-1 at home to the Netherlands.
They remain favourites to win on Wednesday, however, being the second-best team around the globe according to the world governing body FIFA's ranking.
Poland are ranked 26th but will fancy their chances, having one of the world’s top strikers in their side, in captain Robert Lewandowski.
In other team news, winger Jakub Kamiński is expected to start after finding the net as a substitute against Wales.
The match kicks off at 8.45pm.
Poland will then take on the Netherlands in Rotterdam on June 11, in matchday three of the Nations League.
On June 14, Poland will face off against Belgium on home turf in Warsaw.
The UEFA Nations League
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 FIFA World Cup
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, TVP Sport