The aim of this research is to improve the electrochemical performance of the TiO2 anode of lithium-ion battery (LIB). The micro-arc oxidation technology was employed to prepare a TiO2 film on the Ti foil, and then Si/SiO2 was deposited on the TiO2 film by magnetron sputtering technology to prepare a silicon-containing micro-arc oxidation composite film. This composite film was used as the anode of the LIB and a Li foil was used as the counter electrode. The capacity, cycling stability, cyclic voltammetry curves and electrochemical impedance spectra were measured by the battery test system and electrochemical workstation. The experimental results showed that the composite film was composed of TiO2/SiO2/Si with a porous morphology. TiO2, SiO2 and Si all participated in the redox reactions with Li+. After 100 cycles under a current density of 100 μA/cm2, the capacity remained at about 530 (mA.h)/g. Moreover, after cycling under a high current density of 1000 μA/cm2, the capacity can come back to 95% of the initial capacity. This suggests that the prepared TiO2/SiO2/Si composite film has an excellent rate capability with stable structural retention, and its electrochemical performance is much better than that of the TiO2 anode. Therefore, the micro-arc oxidation technology can produce porous and binder-free TiO2 anode materials on the surface of titanium foil with high efficiency. It can also combine with the magnetron sputtering technology to prepare high capacity composite film anodes, which has a bright prospect of industrial application.