The effect of copper oxide species on the CuO–NiO/CeO 2 structure and the influence on the preferential CO oxidation in H 2 excess (CO-PROX) reaction at low and high temperatures were investigated. Temperature-programmed surface reaction (TPSR), In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and X-ray photoelectron spectroscopy (XPS) results allowed determining the surface species. The maximum temperature of CO 2 formation or selectivity decreased about 40 °C for the CuO–NiO/CeO 2 catalyst compared to the NiO/CeO 2 , which suggests that the addition of Cu + species increases the active sites due to interaction with the Ni–Ce structure. Therefore, the activity of the catalyst was closely related to the oxygen in vacancies and the formation of Cu + -carbonyl species of the redox mechanism. Besides, the superior selectivity towards CO 2 below 150 °C depends on the carbonyl stabilization at the surface, inhibiting the adsorption and subsequent oxidation of H 2 . Using TPSR and spectroscopic analyzes by DRIFTS and XPS allowed us to propose the reaction mechanisms for low and high temperatures. • Synergistic interaction between dispersed CuO species and Ni–Ce–O solid solution. • The presence of Ce 3+ in CeO 2 indicate formation of oxygen vacancies on the surface. • The activity was closely related to oxygen vacancies and Cu + -carbonyl species. • The temperature of CuNiCeO catalyst decreased about 40 °C compared to the NiCeO. • The oxygen vacancies and Cu + -carbonyl species suggest a multiple-step process.