Energy storage dielectric capacitors based on a physical charge-displacement mechanism have attracted much attention due to their high power density and fast charge–discharge characteristics. How to improve the energy storage capacity of dielectric materials has become an important emerging research topic. Here, antiferroelectric PbZrO₃ films were prepared by chemical solution deposition on Pt/Ti/SiO₂/Si substrates and crystallized by microwave radiation. The effects of microwave radiation on the antiferroelectric properties and energy storage performance were investigated. In contrast to ordinary heating, microwave radiation can crystallize the amorphous PbZrO₃ films into the perovskite phase at 750 °C in only 180 seconds. The PbZrO₃ films have a highly (100)-preferred orientation and dense microstructure, which is beneficial to enhance the stability of antiferroelectric phase and the electric breakdown strength. The PbZrO₃ films show a recoverable energy storage density of 14.8 J cm⁻³ at 740 kV cm⁻¹, which is approximately 40% higher than that of the PbZrO₃ films crystallized by ordinary heating. The results reveal that microwave radiation is an effective method to improve energy storage performance of antiferroelectric films.