The photocatalytic reduction of CO2 to high value organic substances using solar energy is significantly important to resolve both energy crisis and greenhouse effect. Thus so, Ni loaded inverse opal black TiO2 (IO-B-TiO2/Ni) were successfully prepared. Combining slow photon effect of IO material, the faster charge transfer rates caused by the loading of Ni into TiO2 with the hydrogenated disorder layer of the black TiO2 for light harvesting and charge separation, the IO-B-TiO2/Ni can be used as a stable and highly efficiency catalyst for reduction of CO2 . The formation rate of CO of IO-B-TiO2/Ni is 12.1 mu.mol.g(-1).h(-1), which is about 10.1, 5.1 and 2.0 times as P25, IO-W-TiO2 and IO-B-TiO2, respectively.