Abstract As an energy storage and conversion device with high power density and fast charge and discharge speed, dielectric capacitors play an important role in electronic circuits, electric vehicles, pulse power systems, and other fields. This study uses the sol–gel method to grow BaTiO 3 ‐based films on flexible Mica to achieve flexibility of inorganic energy storage films. To improve the energy storage performance of BaZr 0.15 Ti 0.85 O 3 (BZT), the antiferroelectric material PbZrO 3 (PZO) was introduced to prepare BZT/PZO heterostructure multilayer films. The results show that the introduction of the antiferroelectric PZO layer modulates the polarization behavior of the films. The 2BaZr 0.15 Ti 0.85 O 3 /2PbZrO 3 /2BaZr 0.15 Ti 0.85 O 3 (BPB) heterostructure multilayer film has the best energy storage performance, with a maximum saturation polarization ( P m ) intensity of 40.0 µC/cm 2 , and a W rec of 17.4 J/cm 3 and an η of 56.5%. The energy storage performance is stable after 10 7 cycles at a temperature of 25°C∼140°C. It is expected that this work will promote the development of BZT films in the field of flexible electronics.