 This research is aimed to improve the poor electron conductivity of CeO2 as the catalyst support for methanol oxidation. Pt/CeO2 catalyst coated with nitrogen-doped carbon layer has been prepared through a combined microwave-assisted polyol with in-situ carbonization of nitrogen-doped carbon-coating process using polyvinylpyrrolidone as the nitrogen-doped carbon precursor. Electrochemical results show that Pt/CeO2 catalyst coated with nitrogen-doped carbon layer has higher activity than the uncoated Pt/CeO2 catalyst due to more uniform dispersion, electron-donating effects, and the superior electrical conductivity of the CeO2 support enhanced by the nitrogen-doped carbon layer. Further, electrochemical results show that the optimal doped amount of polyvinylpyrrolidone is 20 wt%. The physical characteristics such as high-resolution transmission electron microscopy and X-ray photoelectron spectrometer have confirmed the existence of the nitrogen-doped carbon layer on CeO2.