Lithium ion was introduced into high purity aluminum (99.999%) by hydrotalcite precursor method, and Li/Al composite anodic film was obtained by anodizing. The methods of X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to investigate the properties of the anodic film. The electrochemistry behaviors of composite anodic film were studied by means of potentiodynamic method and electrochemical impedance spectroscopy (EIS). The results showed that the composite anodic film was produced by hydrotalcite precursor method and which is amorphous to X-ray diffraction. The passivation current density of the anodic film in NaCl solution (1mol/L, pH=3, 7, 11) decreased obviously, while impedance value increased sharply. Corrosion resistance of the composite anodic film in NaCl solution was improved by the introduction of Li+ ion.