In this review, we focus on recent advances in the synthesis of polymer-functionalized transition-metal-based nanomaterials and follow this up by discussing their applications in bioimaging diagnosis and cancer therapy. Transition-metal-based nanomaterials show great potential in cancer therapy owing to their intensive near-IR absorption, excellent photothermal conversion efficiency, strong X-ray attenuation, and magnetic properties. Functional polymers are usually introduced by a one-step or multistep method to further endow these nanomaterials with great biocompatibility and physiological stability. Polymer-decorated transition-metal nanomaterials show great potential in multimodal imaging diagnosis (photoacoustic imaging, computed tomography, photoluminescence imaging, positron emission tomography, etc.) and cancer therapy (chemotherapy, photothermal therapy, microwave therapy, radiotherapy, photodynamic therapy). At the end of this review, the prospects of these polymer-decorated transition-metal-based nanomaterials are also discussed.