Polymer dielectrics have wide application in advanced electronic devices and pulsed power systems because of their easy processing, low cost, outstanding flexibility and high breakdown strength (Eb). However, the low energy density (Ue) of polymer dielectrics restricts the miniaturization and integration of dielectric capacitors. Herein, poly(1,4-anthraquinone) with rigid molecular chains was synthesized and introduced into poly(vinylidene fluoride) (PVDF). Benzene rings on the main chains and large steric hindrance in the side chains limit the intramolecular rotation and thus endow poly(1,4-anthraquinone) with rigid chain structure. Moreover, extended π system and delocalization of electrons minimize the energy of polymer chain, which gives poly(1,4-anthraquinone) more prominent durability and stability. The introduction of poly(1,4-anthraquinone) reduces the crystallite sizes of PVDF and strengthens Young’ modulus of the films. Consequently, both high Eb and Ue are achieved and increased by 170% and 62% compared with pristine PVDF, respectively. This research provides a new strategy to prepare PVDF-based dielectric film with superior energy storage performances.