The novel Cu-doped CeO2 (CeO1-xCuxO2-delta) nanotubes as a superior co-catalyst have been primarily fabricated by coupling reflux with thermolysis methods. Then scanning electron microscopy and transmission electron microscopy reveal that the length of nanotube ranges from 200 nm to 700 nm and its diameter is about 80 nm, and interestingly, these nanotubes can orderly build up into the unique 3D nanobundles. After depositing Pt nanoparticles onto the hybrid support consisted of Vulcan XC-72R and CeO1-xCuxO2-delta, a few PtCu alloys appear on the surface of CeO1-xCuxO2-delta nanotubes. Afterwards, correlative evaluations declare clearly that Pt/C-Ce(0.8)Cu(0.2)O(2-delta )catalyst possesses better electrocatalytic performance and CO resistance, and its electrochemical specific surface area (ECSA) is as high as 142.9 m(2).g(-1), which is one of the best outcomes reported up to now. The fortified catalytic performance of Pt/C-Ce0.8Cu0.2O2-delta may be because the introduction of Cu atom improves the electric conductivity and oxygen vacancy of CeO2, moreover, the hollow structure of nanotubes is beneficial to enhance the charge transfer and ECSA. Therefore, this study not only confirms an extremely handy pathway to synthesize the particular structure, but also offers more possibilities for the development of efficient electrocatalyst in methanol oxidation.