A mesoporous Cu-Ce-Al-based material was prepared by a single-step synthesis, performed in n-propanol using aluminum sec-butoxide as Al precursor and metal stearates, both as Cu-Ce sources and structural directing agents. This type of synthetic approach appears to be very efficient for the preparation of highly dispersed Cu-Ce containing particles supported on a structurally ordered alumina with high surface area (>400 m2 g−1) and quite narrow pore size distribution, as confirmed by X-ray powder diffraction, TPR and dispersion data and N2 physisorption. The catalyst was also characterized by XPS and FT-IR measurements of adsorbed CO. The catalytic activity for the preferential oxidation of CO to CO2 (PROX) in H2-rich streams was tested in the 75–200 °C temperature range.