Copper oxide (CuO)-decorated anatase and TiO2(B) dual-phase titania microsphere (CuO/TiO2(AB)) photocatalysts were synthesized using a facile two-step approach. The photocatalytic reduction of CO2 to form methyl formate (MF) in methanol was evaluated. The results indicated that the CuO-decorated dual-phase TiO2 microspheres displayed MF yield of 1800 mu mol.g(-1) under 4 h illumination, higher than other reference photocatalysts, due to its mixed-phase heterojunction structure and larger surface area, thus leading to an enhanced UV-light response, effective separation and low recombination rate of the photoinduced charge carriers. CuO/TiO2(AB) also showed good stability with the MF yield reproducibility greater than 90% in cyclic runs.