Developing thermally conductive polymers is of fundamental interest and technological importance. Common polymers have low thermal conductivities on the order of 0.1 W·m
–1·K
–1and thus are regarded as thermal insulators. Compared with the traditional heat conductors (metals and ceramics), polymers have unparalleled combined properties such as light weight, corrosion resistance, electrical insulation and low cost. Turning polymer insulators into heat conductors will provide new opportunities for future thermal management applications. Polymers may replace many metals and ceramics, serving as lightweight heat dissipators in electronics, refrigerators, and electrical vehicles.
In this review and perspectives, we discuss the research progress of thermal transport mechanisms in polymers and reveal the relations between thermal conductivity and polymer structural parameters such as bond strength, crystallinity, crystallite size, chain orientation, radius of gyration, and molecular weight. We discuss the advanced strategies for developing thermally conductive polymers by both bottom-up and top-down approaches. We highlight how thermally conductive polymers provide new opportunities for thermal management applications. Finally, we emphasize the future challenges to and opportunities for designing and synthesizing polymers with metal-like thermal conductivity and exploring the thermal transport physics in polymers. We believe that the thermally conductive polymers with their unparalleled combination of characteristics (light weight, electrical insulation, easy processability, corrosion resistance, etc.) promise to possess many existing and unforeseen thermal management applications.