Abstract Polyoxometalates (POM) are a class of inorganic metal oxides with distinctive structural characteristics, compositional versatility, high catalytic efficacy, and convenient storage properties. In recent years, POM have shown considerable potential for mimicking enzyme activities. Besides their biological activities, POM have been demonstrated to possess the ability to sense diseases and perform synergistic therapies based on their redox and near‐infrared absorption properties. Similar to the metallic nanoparticles and the organic materials, these inorganic clusters also exhibit distinctive photothermal imaging and therapeutic properties. Based on this, the current review focuses exclusively on the application of POM in the photothermal therapy of tumors. Furthermore, the advantages and the potential issues associated with the current POM‐based nanomaterials in tumor therapy are discussed and analyzed.