The original PC version has notoriously poor support for modern Xbox or PS5 controllers. You may need a tool like X360CE to map your buttons correctly.
You may need to install the DirectX End-User Runtime to provide legacy files the game expects. download-marvel-ultimate-alliance-apun-kagames-zip
Usually, the site hosts the original 2006 PC version rather than the 2016 Activision remaster (which was later delisted from digital storefronts due to licensing issues). Essential Installation Steps The original PC version has notoriously poor support