Polyoxometalates (POMs) are a series of molecular metal oxide clusters, which span the two domains of solutes and solid metal oxides. The unique characters of POMs in structure, geometry, and adjustable redox properties have attracted widespread attention in functional material synthesis, catalysis, electronic devices, and electrochemical energy storage and conversion. This review is focused on the links between the intrinsic charge carrier behaviors of POMs from a chemistry‐oriented view and their recent ground‐breaking developments in related areas. First, the advantageous charge transfer behaviors of POMs in molecular‐level electronic devices are summarized. Solar‐driven, thermal‐driven, and electrochemical‐driven charge carrier behaviors of POMs in energy generation, conversion and storage systems are also discussed. Finally, present challenges and fundamental insights are discussed as to the advanced design of functional systems based upon POM building blocks for their possible emerging application areas. The links between the intrinsic charge‐carrier behaviors of polyoxometalates (POMs) from a chemistry‐oriented view are discussed and their recent ground‐breaking developments in related areas, including molecular‐level electronic devices, solar‐driven, thermally driven, and electrochemically driven energy generation, conversion, and storage systems are reviewed. Finally, present challenges and the fundamental insights for advanced design and self‐assembly of POM building blocks are also discussed.