Multi-walled carbon nanotubes (MWCNT) supported CuO-CeO 2 catalysts were prepared using an impregnation method aided by an ultrasonication treatment. The structural features of the catalysts were extensively characterized by XRD, TGA, H 2 -TPR, XPS, TEM and Raman spectra. The catalytic performance in the preferential oxidation of CO in a H 2 -rich stream was extensively investigated with respect to the influences of Cu/Ce ratios, the different support materials and the presence of CO 2 and H 2 O in the feed stream. In contrast to those supported on other materials, the catalytic performance was greatly enhanced for the MWCNT-supported CuO-CeO 2 catalysts, which was discussed in terms of the synergistic interactions between Cu-Ce mixed oxides and MWCNT. The optimized catalyst with Cu/Ce ratio of 5/5 can achieve the complete CO conversion and high selectivity toward CO 2 in a wider temperature range as well as the favorable performance under the simulated reformatted gas mixture. The deactivation of CuO-CeO 2 catalyst supported on MWCNT with the elevated temperatures was also discussed in relation to the temperature-dependent in situ XAFS spectra during CO-PROX reaction.