Polymer dielectrics are key components for electrostatic capacitors in energy, transportation, military, and aerospace fields, where their operation temperature can be boosted beyond 125 °C. While most polymers bear poor thermal stability and severe dielectric loss at elevated temperatures, numerous linear polymers with linear D‐E loops and low dielectric permittivity exhibit low loss and high thermal stability. Therefore, the broad prospect of electrostatic capacitors under extreme conditions is anticipated for linear polymers, along with intensive efforts to enhance their energy density with high efficiency in recent years. In this article, an overview of recent progress in linear polymers and their composites for high‐energy‐density electrostatic capacitors at elevated temperatures is presented. Three key factors determining energy storage performance, including polarization, breakdown strength, and thermal stability, and their couplings are discussed. Strategies including chain modulation, filler selection, and design of topological structure are summarized. Key parameters for electrical and thermal evaluations of polymer dielectrics are also introduced. At the end of this review, research challenges and future opportunities for better performance and industrialization of dielectrics based on linear polymers are concluded.