BiFeO3/BaTiO3 bi-layer thick films (~1 μm) were deposited on Pt/Ti/SiO2/(100) Si substrates with LaNiO3 buffer layers at 500 °C via a rf magnetron sputtering process. X-ray diffraction (XRD) analysis revealed that both BiFeO3 and BaTiO3 layers have a (00l) preferred orientation. The films showed a small remnant polarization (Pr ~ 7.8 μC/cm2) and a large saturated polarization (Ps ~ 65 μC/cm2), resulting in a slim polarization-electric field (P-E) hysteresis loop with improved energy storage characteristics (Wc = 71 J/cm3, η = 61%). The successful “slim-down” of the P-E loop from that of the pure BiFeO3 film can be attributed to the competing effects of space charges and the interlayer charge coupling on charge transport of the bi-layer film. The accompanying electrical properties of the bi-layer films were measured and the results confirmed their good quality.