Multilayer thin films have been demonstrated to enhance the energy storage performance of dielectric capacitors, due to the synergistic effects of different functional layers in heterostructures. In this Letter, a multilayer structure is proposed based on the Pb(Zr0.52Ti0.48)O3 (PZT) homostructure. It has been experimentally demonstrated that the alternative PZT layer exhibits different crystallinity induced by Ce dopant incorporation. Thus, the polarization and breakdown strength are well balanced, giving rise to a high recoverable energy density of 74 J/cm3 with a high breakdown electric field of 6.49 MV/cm and a relatively large polarization of 28 μC/cm2. The homostructures provide a simple method to construct dielectric multilayer films to promote energy density only via one-step annealing treatment and one type of dielectric material.