The nanostructured Ce ion substituted cryptomelane-type octahedral molecular sieve (OMS-2) catalyst exhibits strong absorption in the entire solar spectrum region. The Ce ion substituted OMS-2 catalyst can efficiently transform the absorbed solar energy to thermal energy, resulting in a considerable increase of temperature. By combining the efficient photothermal conversion and thermocatalytic activity of the Ce ion substituted OMS-2 catalyst, we carried out full solar spectrum, visible-infrared, and infrared light driven catalysis with extremely high efficiency. Under the irradiation of full solar spectrum, visible-infrared, and infrared light, the Ce ion substituted OMS-2 catalyst exhibits extremely high catalytic activity and excellent durability for the oxidation of volatile organic pollutants such as benzene, toluene, and acetone. Based on the experimental evidence, we propose a novel mechanism of solar light driven thermocatalysis for the Ce ion substituted OMS-2 catalyst. The reason why the Ce ion substituted OMS-2 catalyst exhibits much higher catalytic activity than pure OMS-2 and CeO2/OMS-2 nano composite under the full solar spectrum irradiation is discussed.