Semiconductor-based photocatalytic carbon dioxide ( CO2) reduction is of great scientific importance in the field of alleviating global warming and energy crisis. Surface amine modification and cocatalyst loading on the catalyst surface could improve CO2 adsorption capacity and photogenerated charge separation. Herein, amine-modified brookite–TiO2 ( NH2–B–TiO2) coupled metal species (Cu, Ag, Ni(OH)2) cocatalysts have been successfully synthesized by chemical reduction method. The photocatalytic CO2 reduction results show that the CH4 production rates of NH2– B–TiO2/Cu, NH2– B–TiO2/Ag, and NH2– B–TiO2/Ni(OH)2 are 3.2, 12.5, and 1.7 times that of NH2– B–TiO2 (0.74 μmmol g− 1 h− 1), respectively. Results show the introduction of metal species on the surface of the catalyst enhances the absorption range of sunlight and the photogenerated carrier separation efficiency, resulting in enhancing the performance of photocatalytic CO2 reduction. This work provides a strategy for designing metal species-loaded amine-modified brookite–TiO2 by surface/interface regulation to improve photocatalytic efficiency.