The photocatalytic conversion of CO2 to renewable hydrocarbon fuels by solar energy is important in solving both energy and environmental problems. In this study, highly robust hybrid systems (H-Bi2WO6/MnP, F-Bi2WO6/MnP, and T-Bi2WO6/MnP) for visible-light reduction of CO2 to CO were developed. A Mn complex was anchored to Bi2WO6 particles via bisphosphonate functional groups. Photocatalytic CO2 reduction with this catalytic system under visible-light (lambda > 400 nm) irradiation was investigated. CO was the only product, i.e., no other products were detected in the present system. The addition of water or triethylamine significantly enhanced the CO2 conversion activity of the hybrid photocatalytic system. The addition of 25% (v/v) water enhanced the photocatalytic CO2 reduction efficiency of H-Bi2WO6/MnP. A turnover number of 301 for 8 h was achieved, compared with 255 for F-Bi2WO6/MnP and 212 for T-Bi2WO6/MnP. The Mn complex played an important role in achieving highly selective conversion of CO2 to CO. A possible mechanism, namely a "Z-scheme", for CO2 reduction is proposed. These results confirm that the H-Bi2WO6 semiconductor is an essential component in our heterogeneous hybrid system. It effectively acts as a photosensitizer, an electron reservoir, and an electron transport mediator. (C) 2019 Elsevier Ltd. All rights reserved.