Abstract: Polymer film capacitors are widely used in electrical equipment and electronic devices due to the advantages of high density, high pulse current, low cost, and easy processing. In recent years, material systems have been enriched in polymer capacitive films, and the modification methods such as nano/micro-nano functional filler composite, polymer molecular chain structure control, and mesoscopic/macroscopic multilayer interface design have been used to significantly improve the discharge energy density and charge/discharge efficiency of polymer films. The energy storage performance of polymer composite films based on multilayer structure design has received great attention. This paper reviews the recent progress in the field of polymer energy storage dielectrics based on multilayer structure design, the mechanism of multilayer structure design on the properties of composite films such as polarization, breakdown and high temperature conductivity are systematically introduced, and the methods for improving energy storage performance are summarized from three aspects, namely, nanocomposite multilayer structure, all-organic multilayer structure, and high temperature resistant multilayer structure. Finally, a brief outlook on the future development of composite films with multilayer structure design is given.