Abstract: Thermally conductive polymer composites have been widely applied in various industries due to lightweight, flexible design and easy-processing. However, the thermal conductivity k and dielectric breakdown strength E_b of polymer composites cannot be synergistically enhanced, thereby seriously affecting and limiting their applications in the high-voltage power equipment. The intrinsic thermally conductive polymers (ITCP) resulting from the developed ordered structures based on pristine discorded structures, not only reserve inherent excellent overall properties, but also exhibit a concurrent enhancement in both E_b and k. This paper discussed the heat conduction mechanism and analyzed the factors influencing k of intrinsic polymers, and summarized the latest advances in ITCP. Furthermore, the factors influencing k, such as polymer structure, orientation, hydrogen bonding, mesomorphic unit and curing agents, processing methods, were analyzed, as well as the strategies to improve the ordered arrangement and k of polymer microstructures. Finally, this paper summarized the existing questions in the study of ITCP and pointed out the future research direction of ITCP. The ITCP show important applications in high-density electronic packaging and high-voltage power equipment, representing the future development direction of thermally conductive polymer composites.