Wales last faced Poland in 2016, drawing a Cyprus Cup friendly 1-1 with a goal from Helen Ward.
The Poles, under head coach Nina Patalon, were also making their bow on the major international stage at Euro 2025, where they lost to Germany and Sweden before beating Denmark 3-2 to finish third in Group C.
Wales lost all three of their games, finishing bottom of Group D after defeats against Netherlands, France and England.
The two friendly fixtures in October will mark the beginning of preparations for 2027 World Cup qualifying, which will take place from February to December 2026.
The draw for the European qualifying tournament for Brazil 2027 is scheduled to take place on 4 November, 2025.
Both the match against Poland and the game with Australia on Saturday, 25 October (14:00 BST) will be live on BBC One Wales, BBC iPlayer, the BBC sport website and app, BBC Radio Wales and BBC Radio Cymru.