The photocatalytic reduction of CO2 could be achieved over Cu/S-TiO2 under UV and visible light irradiation. S-TiO2 was fabricated via calcination of TiO2 precursor and thiourea, Cu species were plated on the surface of S-TiO2 by electroless plating method. XRD revealed that S-TiO2 was anatase phase, UV-Vis absorption spectrum showed an excellent visible light absorption of Cu/S-TiO2. Cu species plated on S-TiO2 by electroless plating method could facilitate the photogenerated charges capture, separation and transfer. The products of CO2 photocatalytic reduction involved gas phase of methane, carbon monoxide and hydrogen, and liquid phase of methanol, formic acid and acetic acid. The in-situ IR spectra indicated that the OH radical acted as an intermediate participating in the photocatalytic reaction.