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.