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Al specimens were covered with TiO2 film by sol-gel dip-coating and then anodized in ammonium adipate solution. The structure, composition and capacitance properties of the anodic oxide film were investigated by transmission electron microscopy (TEM), Auger electron spectroscopy (AES), X-ray diffractometry (XRD) and electrochemical impedance spectroscopy (EIS). It was found that an anodic oxide film with a dual-layer structure formed between TiO2 coating and Al substrate. The film consisted of an inner Al2O3 layer and an outer Ti-Al composite oxide layer. The thickness of layers varied with the number of times of sol-gel dip-coating. The capacitance of anodic oxide films formed on coated specimens was at most 80% higher than that without TiO2. In film formation mechanism, it was claimed that the formation of composite oxide film was mainly affected by the structure of micro-pores network in TiO2 coating which had an influence on Al3+ and O2- ions transport during the anodizing.