CO-SCR was considered as one of the most optimum technologies for synergistic removal of nitrogen oxides and carbon monoxide from flue gas. CuCe catalyst showed excellent NOx and CO catalytic activity in the range of 250–500 °C because of its unique physicochemical property. Herein, the mechanism of CuCe catalyst in the CO-SCR reaction at different temperature was studied via in situ DRIFTS characterization. The result indicated that the adsorbed CO species could react with gaseous NO molecules over CuCe catalyst at 150 ºC, implying that the E-R mechanism was obeyed at lower temperature. Moreover, the nitrate/nitrite species and adsorbed CO species could react with each other on the surface of CuCe catalyst at 350 ºC, indicating that the L-H mechanism was followed in the CO-SCR reaction at higher temperature. This work proposed the reaction mechanism of CuCe catalyst at different temperature for NO reduction by CO, which could provide a theoretical direction for the optimization of CuCe catalyst and promote its application in industrial production.