Ordered Co3O4 with high surface area (until 173 m(2)/g) has been successfully obtained through a nanocasting route using mesoporous KIT-6 silica as a hard template and tested in the deep oxidation of a series of representative volatile organic compounds (VOCs): propane as a model of short chain alkane and toluene as a model of monoaromatic hydrocarbon. It has been demonstrated that the catalytic activity for VOC deep oxidation is very elevated and its catalytic stability at moderate temperatures very good. However, the role of the ordered structure in the catalytic performance does not seem to be beneficial. The enhanced catalytic activity has been explained in terms of both the high surface area and the presence of oxygen vacancies. In the present work we show for the first time the catalytic behaviour of a nanocasted cobalt oxide for the elimination of different VOCs. (C) 2010 Elsevier B.V. All rights reserved.