A series of copper-modified titanium dioxide (Cu/TiO2) nanoparticles were synthesized via one-step sol-gel method. The crystal structure and chemical properties were characterized using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The Cu/TiO2nanoparticles were applied to CO2photoconversion and the yield of formaldehyde was used to evaluate the photocatalytic performance. The optimum amount of copper modifying was 0.6 wt.% and the yield of formaldehyde was 946 μmol/gcatunder UV illumination for 6 h. 20 wt.% Cu/TiO2also performed a high photocatalytic activity, which yielded 433 μmol/gcatformaldehyde under UV illumination for 6 h.