Inorganic ferroelectric perovskites are attracting attention for the realization of highly stable photovoltaic cells with large open-circuit voltages. However, the power conversion efficiencies of devices have been limited so far. Here, we report a power conversion efficiency of ~4.20% under 1 sun illumination from Bi–Mn–O composite thin films with mixed BiMnO3 and BiMn2O5 crystal phases. We show that the photocurrent density and photovoltage mainly develop across grain boundaries and interfaces rather than within the grains. We also experimentally demonstrate that the open-circuit voltage and short-circuit photocurrent measured in the films are tunable by varying the electrical resistance of the device, which in turn is controlled by externally applying voltage pulses. The exploitation of multifunctional properties of composite oxides provides an alternative route towards achieving highly stable, high-efficiency photovoltaic solar energy conversion.