Bimetal oxides derived from metal-organic-frameworks, by means of either one-step or post-treated method, have been extensively studied so far. However, for the same kind of bimetal oxides prepared from different methods stated above, their comparison in catalytic reactions has rarely reported. In this work, two kinds of CeO2-CuO catalysts derived from Ce-MOF are prepared, and their catalytic activities toward CO oxidation are compared as well. Based on the X-ray diffraction, X-ray photoelectron spectroscopy, Brunaue-Emmett-Teller, temperature programmed reduction, UV-Raman, and in-situ diffuse reflectance infrared Fourier transform spectroscopy characterizations, we found MOF-derived CeO2-CuO catalysts obtained from one-step and post-treated methods exhibit different synergistic interactions between components, thus resulting in different catalytic activities toward CO oxidation.