Abstract: A simple and convenient method for preparing CuO-doped CeO₂ hollow spheres via PS templates was presented. The structural characteristics of CuO/CeO₂ hollow spheres were characterized by scanning electron microscopy (SEM), Energy Dispersive Spectrometer (EDS), X-ray diffraction (XRD), N₂ adsorption-desorption isotherm and X-ray photoelectron spectroscopy (XPS). To evaluate the differences of catalytic properties among the CuO/CeO₂ hollow spheres, industrial CeO₂ and CeO₂ hollow spheres, H₂-temperature programmed reduction (H2-TPR) and CO oxidation tests were carried out. The results show that the synthesized samples have good morphology, large specific surface area and high purity. The H₂-TPR analysis reveals that the reducibility of CuO/CeO₂ hollow spheres has diverse surface oxygen species. CuO doped CeO₂ hollow spheres exhibit better performance than CeO₂ hollow spheres and commercial CeO₂ in CO oxidation in that the copper can effectively enhance the catalytic activity of the samples for CO oxidation through the increase of peroxide defects and synergistic effect.