This study aims to extend the light spectrum which could be absorbed by TiO2 to infrared ray light (IR) by loading P4O10 in order to promote the CO2 reduction performance of TiO2 photocatalyst. Three ranges of light with P4O10/TiO2 film are studied, which are ultra violet light (UV) + visible light (VIS) + IR, VIS + IR, and IR only. This study also investigates the impact of molar ratio of CO2/H2O or CO2/NH3 on the CO2 reduction characteristics of P4O10/TiO2 film. The largest CO2 reduction performance in case of CO2/H2O and CO2/NH3 is obtained at CO2:H2O = 1:1 and CO2:NH3 = 3:2 respectively, irrespective of light illumination condition. With IR light illumination only, the largest molar quantity of CO per unit weight of photocatalyst for P4P10/TiO2 film in case of CO2/H2O and CO2/NH3 is 2.36 mmol/g and 33.4 mmol/g, respectively.