Surface modification of nanoceramics with high dielectric constant can increase dielectric constant of polymer composites voiding excessive dielectric loss, however, low discharged energy density (Ud) of composites at a low loading limits potential applications in high–energy–storage devices under low electric field. Herein, Ni–plated CaCu3Ti4O12 nanoparticle (CCTO@Ni) is used to improve the electric properties of the poly(vinylidene fluoride) monolayer composites (C/PVDF), and an ultralow loading of 0.5 vol% promotes the largest Ud of 2.53 J/cm3 at 230 MV/m, resulting from MWS interface polarization and Coulomb barrier effect included by CCTO@Ni fillers, which is used to further prepare three kinds of multi–layer structured C/PVDF composites by solution casting layer by layer. Comprehensive testing shows that the PVDF–C/PVDF–PVDF–C/PVDF–PVDF five–layer film (P–C–P–C–P) enhances the dielectric constant and breakdown strength to contribute the maximal Ud of 6.65 J/cm3 at 297.8 MV/m, which is 118% larger than that of pure PVDF. Above excellent characteristics are attributed to the interface polarization of the middle C/PVDF layer and the alleviating and blocking effect of the middle and outer PVDF layers, which are clarified in depth by the finite element simulation and enhanced breakdown model.