Aerospace, electric vehicles, and other particular application scenarios place higher demands on the applicable electric field and temperature of capacitors. Polyimide, as the most ideal and widely studied high-temperature capacitor dielectric material, has poor insulation performance under extreme conditions. The main reason is that many conjugated π-bonds on its aromatic rings provide channels for the movement of free electrons, this phenomenon is more intense in high-temperature and high-field environments, which accelerates the high-temperature performance degradation of polyimide. Herein, we propose a molecular structure strategy to design high-temperature capacitance performance polymer dielectrics based on the induction effect. Both the experimental and density functional theory calculation results indicate that the polar functional groups -CF3 and –OCH3 can lead to a strong induction effect, which changes the direction of electron transport on the aromatic ring, serve to weaken the free-sharing ability of electrons in the conjugated π bond, increases the energy levels of PI and induces the formation of local deep traps in the polymer films, which significantly restrains charge carrier transport, ultimately improves the high-temperature capacitance property for aromatic polyimide. The resultant polymer film exhibits an excellent discharged energy density (Ud) of 7.9 J/cm3 at 150 °C and 810.3 MV/m. Meanwhile, it maintains excellent stability at over 100,000 fatigue tests and 500 MV/m. Hopefully, it will provide theoretical and technical support for developing high-performance capacitors.