Abstract: Polymer dielectric materials are widely used in power systems due to their low cost, high breakdown strength and high reliability. However, polymer dielectric materials have relatively low discharge energy density, making it difficult to meet the requirements of next-generation miniaturized capacitors. Multilayer structures show the advantage of synergistically improving the dielectric permittivity and breakdown strength, thus solving the contradiction between the dielectric permittivity and breakdown strength of polymer dielectric materials, and achieving polymer-based dielectric materials with excellent energy storage performance. This article reviews the progress in researching polymer-based composite materials with multilayer structures in recent years, analyzes the polarization and breakdown phenomena in multilayer structures, discusses in detail the design of polymer-based multilayer structures and multilayer structures combining inorganic layers with polymer-based layers, and summarizes some methods that can enhance the energy storage of multilayer structure polymer-based composite materials. For example, energy storage properties are enhanced by adding interfaces, optimizing filler distribution in multilayer structures and building transition layers. Finally, the progress of polymer-based composite materials with multilayer structures in recent years is summarized, and future development and issues to be addressed are proposed.