Polymers are the preferred materials for dielectrics in high-energy-density capacitors. The electrification of transport and growing demand for advanced electronics require polymer dielectrics capable of operating efficiently at high temperatures. In this review, we critically analyze the most recent development in the dielectric polymers for high-temperature capacitive energy storage applications. While general design considerations are discussed, emphasis is placed on the elucidation of the structural dependence of the high-field dielectric and electrical properties and the capacitive performance, including discharged energy density, charge-discharge efficiency and cyclability, of dielectric polymers at high temperatures. Advantages and limitations of current approaches to high-temperature dielectric polymers are summarized. Challenges along with future research opportunities are highlighted at the end of this article.