Dielectric capacitors have been developed for nearly a century, and all‐polymer film capacitors are currently the most popular. Much effort has been devoted to studying polymer dielectric capacitors and improving their capacitive performance, but their high conductivity and capacitance losses under high electric fields or elevated temperatures are still significant challenges. Although many review articles have reported various strategies to address these problems, to the best of current knowledge, no review article has summarized the recent progress in the high‐energy storage performance of polymer‐based dielectric films with electric charge trap structures. Therefore, this paper first reviews the charge trap characterization methods for polymeric dielectrics and discusses their strengths and weaknesses. The research progress on the design of charge trap structures in polymer dielectric films, including molecular chain optimization, organic doping, blending modification, inorganic doping, multilayered structures, and the mechanisms of the charge trap‐induced enhancement of the capacitive performance of polymers are systematically reviewed. Finally, a summary and outlook on the fundamental theory of charge trap regulation, performance characterization, numerical calculations, and engineering applications are presented. This review provides a valuable reference for improving the insulation and energy storage performance of dielectric capacitive films.