Enhancing the performance of TiO2 material in lithium-ion battery application is a promising objective. According to the photo-electrochemical activity of TiO2, herein we develop a novel and facile photo-deposition strategy to synthesize Co3O4/TiO2 composites by using TiO2 nanotubes as substrate material and ultraviolet light as energy source. The physical characterizations indicate that after the proposed procedures small-sized Co3O4 nanoparticles are well deposited on the surface of TiO2 nanotubes to form a Co3O4 layer that distributed all through the tubes. As anode materials for lithium storage, the as-synthesized Co3O4/TiO2 nanotube composites exhibit enhanced performance with higher capacity and rate capability at various test current densities than bare TiO2 nanotubes. The improved performance of composite products is mainly attributed to the coating of Co3O4 layer which can not only increase the conductivity of TiO2, but also could contribute to the overall reversible capacity during charge/discharge.