This work is mainly focused on investigating the effects of different doped metal cations on the formation of Ce20M1Ox (M=Zr, Cr, Mn, Fe, Co, Sn) composite oxides and their physicochemical and catalytic properties for NO reduction by CO as a model reaction. The obtained samples were characterized by using N-2 physisorption, X-ray diffraction, laser Raman spectroscopy, UV/Vis diffuse reflectance spectroscopy, inductively coupled plasma atomic emission spectroscopy, X-ray photoelectron spectroscopy, temperature-programmed reduction by hydrogen and by oxygen (H-2-TPR and O-2-TPD), insitu diffuse reflectance infrared Fourier transform spectroscopy, and the NO+CO model reaction. The results imply that the introduction of Mx+ into the lattice of CeO2 increases the specific surface area and pore volume, especially for variable valence metal cations, and enhances the catalytic performance to a great extent. In this regard, increases in the oxygen vacancies, reduction properties, and chemisorbed O-2(-) (and/or O-) species of these Ce20M1Ox composite oxides (M refers to variable valence metals) play significant roles in this reaction. Among the samples, Ce20Cr1Ox exhibited the best catalytic performance, mainly because it has the best reducibility and more chemisorbed oxygen, and significant reasons for these attributes may be closely related to favorable synergistic interactions of the vacancies and near-surface Ce3+ and Cr3+. Finally, a possible reaction mechanism was tentatively proposed to understand the reactions.