This work is mainly focused on the investigation of the influence of Mn-doped CeO2 supported by CuO on the physicochemical and catalytic properties for CO oxidation and NO + CO model reaction. The obtained samples were characterized using N-2-physisorption (BET), XRD, LRS, TEM, EDS-Mapping, ICPAES, XPS, H-2-TPR, O-2-TPD, in situ DRIFTS, CO oxidation, and NO + CO model reaction. The results imply that appropriate doping MnOx into the lattice of CeO2 will cause an obvious change in the properties of the catalyst and the Cu/CeMn-10: 1 catalyst shows the largest specific surface area, the most uniformity of structure, and the most extent of lattice expansion. A few addition of MnOx is more conducive to the generation of low valence manganese ion in the process of calcination, which may contribute to the synergetic introduction. This further results in more Cu+ due to the shifting of redox equilibrium (Cu2+ + Ce3+ <-> Cu+ + Ce4+) to right, as well as more oxygen vacancies. Moreover, the capability of Cu/CeMn-10: 1 on desorb/transform/decompose of the adsorbed NO species is more effective than that of Cu/CeO2. The results of catalytic performance show that Cu+/Cu-0 species play a key role, and the activity is mainly related to the specific surface area, the content of Cu+ and Ce3+, the reduction, desorption capability of chemisorbed O-2(-) (and/or O-) species as well as adsorption behaviors of these catalysts for CO oxidation and NO + CO reaction. Finally, possible reaction mechanisms are tentatively proposed to understand the reactions. (C) 2016 Elsevier B.V. All rights reserved.