Pure polymer film dielectrics with the evident advantage of easy fabrication have been widely used in electronic and electrical systems. But their application is restricted from many high-end fields, such as power electronics and pulsed power devices in which the working temperature is upto 200 °C, where the energy density becomes much lower than that at room temperature. Herein, compact polymer films with a smooth surface are elaborately fabricated through “The King of Plastic” polytetrafluoroethylene (PTFE) nanoparticles by a simple yet effective strategy of heat-treatment. Ultrahigh charge-discharge efficiency (η~94%) and electric breakdown strength (αb~350 kV/mm) are achieved at a high temperature of 200 °C, which result in a high discharged energy density (Ud~1.08 J/cm3) and a high power density (Pd0.9~0.72 MW/cm3). The state of the art performance of the dielectric and energy storage is attributed to the symmetric molecular structure, compact microstructure and smooth surface of the PTFE films. Importantly, the PTFE films coated with Au electrode perform excellent self-healing ability at high temperatures. The elaborately fabricated PTFE film is thus ideal for high-temperature energy storage application and it also can be used as polymer matrix for holding fillers to acquire even higher performance.