Ferroelectric photovoltaic oxides have attracted extensive attention for low-cost solar cells owing to high structure stability and abundant resources. In this paper, we report new perovskite ferroelectric material Na0.5Bi0.5FeO3 featuring low band gap derived from oxygen vacancies induced by high content Na substitute in A-sites. Solution-processed heterojunction solar cell based on Na0.5Bi0.5FeO3 film with Spiro-OMeTAD as the hole transporter is fabricated, of which photovoltaic properties is found to be significantly improved by pre-polarization treatment. It is demonstrated that the photovoltaic properties of Na0.5Bi0.5FeO3 solar cell are affected by both charge transport dynamic and interfacial charge recombination tuned by ferroelectric polarization. (C) 2018 Elsevier B.V. All rights reserved.