Abstract: With CNT@TiO₂ prepared by sol-gel method as the support, the PtCo-CNT@TiO₂ composite was prepared by electro-deposition and used as the anode catalyst for direct methanol fuel cells. The PtCo-CNT@TiO₂ composite was characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and electrochemical workstation. The results show that the PtCo-CNT@TiO₂ composite displays significant crystals and the metal particles surround the TiO₂-coated carbon nanotubes; when used as the anode catalyst for direct methanol fuel cells, it exhibits high activity and stability. The PtCo-CNT@TiO₂ catalyst has an electrochemical surface area of 164 m²/g and the oxidation peak current of methanol reaches 45 mA/cm² at 65 ℃; after 300 s, the oxidation current tends to be 24 mA/cm² and the oxidation peak current of methanol under alkaline conditions is 39.7 mA/cm².