Abstract Polymer dielectrics are indispensable for high‐energy‐density capacitors due to their lightweight, mechanical flexibility, and excellent processability. However, most existing polymer dielectrics suffer from limited operating temperatures, which significantly restricts their application in emerging fields such as electrified transportation, aerospace electronics, and compact high‐power systems, where reliable operation under elevated temperatures and high electric fields is crucial. With increasing device integration and power density, there is a growing demand for polymer dielectrics capable of sustaining high energy storage performance under simultaneous thermal and electrical stress. This review summarizes the latest advances in high‐temperature all‐organic polymer dielectrics and provides fundamental insights to guide molecular design and structural engineering for capacitive energy storage under extreme conditions. While key structural parameters influencing capacitive behavior are discussed, emphasis is placed on the interplay between molecular structure, dielectric properties, and energy storage performance. The advantages and limitations of current approaches to high‐temperature all‐organic polymer dielectrics are critically evaluated. Finally, the review outlines the remaining challenges and future opportunities for advancing the development of high‐performance all‐organic polymer dielectrics capable of delivering reliable, efficient high‐temperature energy storage.