Abstract: With the development of miniaturization, high power and integration of electronic and electrical equipment, the functional and diversified demands for dielectric capacitors need to be increasingly met. Therefore, higher requirements are posed to energy storage dielectric materials for capacitors to adapt to more increasingly complex working environment. As an engineering plastic with excellent characteristics such as high temperature resistance, chemical corrosion resistance, and high thermal stability, polyimide is considered as a candidate material for high temperature resistant energy storage dielectric films. However, due to its relatively low dielectric permittivity, it has greatly affected its application as a high-temperature energy storage dielectric. According to the relationship between molecular structure and performance, the compromise of dielectric performance and heat resistance can be achieved by adjusting the space structure and configuration. Therefore, how to improve the dielectric and energy storage properties of polyimide intrinsically has become one of the key issues in the field that needs to be solved urgently. Based on the mechanism of improving the energy storage characteristics of polyimide, we analyzed the strategies for improving the energy storage characteristics of intrinsic high-temperature-resistant polyimide dielectric materials from the perspective of molecular structural design, including polymer molecular structure, synthesis of new monomers, polymer-metal complexation, and copolymerization modification. Finally, the current high-temperature energy storage polyimide dielectric research is summarized and the future development direction is expected, in order to realize the research and development of polymer films with excellent energy storage characteristics for next-generation capacitors.