In this study, we present an efficient strategy, that is the co-substitution of Fe3+ and Ta5+ ions with large radius for Ti4+ ion, to enhance energy storage performance of Ba2Bi4Ti5O18 film. For the films co-doped with Fe3+ and Ta5+ ions, the maximum polarization under the same external electric field is improved because the radius of Fe3+ and Ta5+ ions is larger than that of Ti4+ ion. Moreover, due to the composition and chemical disorder, the relaxor properties are also slightly improved, which can not be achieved by the film doped with Fe3+ ions only. What’s more, for the films doped with Fe3+ ion only, the leakage current density increases greatly due to the charge imbalance, resulting in a significant decrease in breakdown strength. It is worth mentioning that the breakdown strength of Fe3+ and Ta5+ ions co-doped film does not decrease due to the charge balance. Another important point is the recoverable energy storage density of the films co-doped with Fe3+ and Ta5+ ions have been greatly improved based on the fact that the maximum external electric field does not decrease and the maximum polarization under the same external electric field increases. On top of that, the hysteresis of the polarization has also been improved. Finally, the co-doped films with Fe3+ and Ta5+ ions have good frequency and temperature stability.