A literature review on the thermal spray deposition of metals onto polymer-based structures is presented. The deposition of metals onto polymer-based structures has been developed to enhance the thermal and electrical properties of the resulting metal-polymer material system. First, the description of the thermal spray metallization processes and technologies for polymer-based materials are outlined. Then, polymer surface preparation methods and the deposition of metal bond-coats are explored. Moreover, the thermal spray process parameters that affect the properties of metal deposits on polymers are described, followed by studies on the temperature distribution within the polymer substrate during the thermal spray process. The objective of this review is devoted to testing and potential applications of thermal-sprayed metal coatings deposited onto polymer-based substrates. This review aims to summarize the state-of-the-art contributions to research on the thermal spray metallization of polymer-based materials, which has gained recent attention for potential and novel applications.