The effects of different components in Cu 1Zr 1Ce 9O δ catalyst and the variations of the feed stream on the catalytic performance of selective CO oxidation were investigated by diffuse reflectance infrared Fourier-transform spectroscopy (DRIFTS) technique. It is found that the active sites of Cu 1Zr 1Ce 9O δ catalyst are mainly Cu + species. Formate species is formed through the reaction between CO gas and hydroxyl groups on the reduced cerium surface. CeO 2 in the Cu 1Zr 1Ce 9O δ catalyst facilitates the formation of Cu + species and improves the amount of CO adsorption whereas it is unfavorable to the deep reduction of Cu + species. ZrO 2 doped into the Cu 1Zr 1Ce 9O δ catalyst increases the Cu coverage and CO adsorption capacity, while it decreases the adsorption of CO 2 on the catalyst surface. The adsorption capacities of oxygen and CO are associated with the catalytic performance for the selective CO oxidation at lower and higher temperatures, respectively. The presence of CO in the feed stream promotes the reduction of Ce 4+ species and the production of geminal OH group on the reduced ceria surface. Hydrogen in the feed diminishes the CO adsorption ability but stimulates the CO desorption. CO 2 in the feed occupies the active sites and decreases the adsorption of the reactants, thus deteriorates the catalytic performance for the selective CO oxidation.