TiO2 is an attractive anode material for Li-ion batteries due to its high capacity, high mechanical stability during Li intercalation/deintercalation process, limited side reactions with the electrolyte, low cost, and environmental friendliness. In this study, titanium hydroxide gel films were prepared in acidic aqueous solutions of TiOSO4, H2O2 and KNO3 by potentiostatic cathodic electrosynthesis on various copper substrates, including planar Cu foil, mechanically polished planar Cu foil, and Cu nanorod arrays grown on Cu foil. Crystalline TiO2 films were obtained by heat treating the electrodeposited titanium hydroxide gel films at 500 oC in argon atmosphere. The morphology and microstructure of the TiO2 films were characterized by scanning electron microscope (SEM) and X-ray diffraction (XRD). SEM results showed that after deposition, each Cu nanorod has been covered by a layer of TiO2 gel, forming a core-shell structure. The effects of Cu nanorod arrays on the morphology and the electrochemical property of the TiO2 deposits were discussed.