Photoreduction of CO2 to fuels and chemicals is a challenging reaction mainly due to the poor conversion and selectivity of the desired products. Although many semiconducting materials have been explored hitherto for the CO2 photoreduction, insignificant product yields, insufficient visible light absorption, and least charge separation made them of limited applicability. Herein, we demonstrated the synthesis, physicochemical characterization, and photocatalytic evaluation of heterojunction composite consisting of spherical Fe- and hexagonal Ni-doped CeO2 nanorods to reduce CO2 into methanol selectively under visible irradiation. The developed heterojunction exhibited excellent activity and afforded a maximum of 7039 μmol-g−1 of methanol in 24 h of irradiation using triethylamine as a sacrificial donor. The developed photocatalyst exhibited higher activity than the previously reported ceria-based systems for CO2 reduction. Notably, the photocatalyst was found to be robust that could be reused at least for five runs without any significant loss in the methanol yield.