Ceria catalysts have been prepared by a nanocasting procedure using SBA-15, MCM-48 and KIT-6 silica-based templates, and investigated for the total oxidation of naphthalene. In all cases cubic fluorite CeO2 was prepared, and the structure of the template was replicated when SBA-15 and MCM-48 were used. The KIT-6 template was not replicated by the nanocasting synthesis, but in all cases mesoporous CeO2 was obtained with high surface areas (91–190 m2 g−1). All of the catalysts demonstrated high activity for naphthalene oxidation to CO2, and the most active was the catalyst prepared from the KIT-6 template. The high activity was attributed to the small crystallite size of the CeO2, combined with high surface area and the highly accessible catalyst surface.