A Ce–Zr–Cu oxide system with a flower-like morphology was prepared by a slow co-precipitation method in the absence of any structure directing agent. Four portions of the oxide were thermally treated at four different temperatures (350°C, 450°C, 550°C, 650°C). The resulting materials samples were characterized by quantitative XRD, adsorption–desorption of N 2 at-196°C, SEM and TEM microscopy, –H 2 -TPR, XPS and Operando-XANES. All samples were tested in the preferential CO oxidation (CO-PROX) in the 40–190°C temperature range. Thermal treatments were found to induce slight structural changes without altering the starting morphology of the samples. The samples treated at higher temperature 550–650°C showed a quite interesting CO-PROX activity and selectivity in a temperature range suitable for a practical use within the FEMFC technology.