Herein, a series of metal oxide/CeO₂ (M/CeO₂) nanocomposites derived from Ce-benzene tricarboxylate (Ce-BTC) adsorbing with different metal acetylacetonate complexes were prepared for CO oxidation under four different CO gas atmospheres. It was demonstrated that Cu/CeO₂ exhibited the highest catalytic activity and stability in CO oxidation. Remarkably, both O₂ selectivity and CO selectivity to CO₂ are 100% in most of the investigated conditions. Several analytical tools such as N₂ adsorption–desorption and powder X-ray diffraction, were employed to characterize the prepared catalysts. In addition, the excellent catalytic performance of Cu/CeO₂ in CO oxidation was revealed by H₂ temperature-program reduction experiment, X-ray photoelectron spectroscopy, and in situ diffuse reflectance infrared Fourier transform spectroscopy. The result showed that high oxygen vacancy and high CO adsorption capacity (Cu⁺–CO) caused by the electron exchanges of Cu²⁺/Cu⁺ and Ce³⁺/Ce⁴⁺ pairs (Ce⁴⁺ + Cu⁺ ⇆ Ce³⁺ + Cu²⁺) are two key factors contributing to the high oxidation performance of Cu/CeO₂ catalyst.