Two V-SBA-15 and V-MCF materials (V content ca. 2.5 wt.%) were prepared by direct synthesis and tested in the catalytic decomposition of dichloromethane. Their catalytic properties were compared to those of other materials with the same vanadium content, namely two mesoporous materials prepared by impregnation (V-SBA-15-i and V-MCF-i) and a non-porous one prepared by flame pyrolysis (V-SiO(2)). Both direct synthesis and flame pyrolysis methods allowed a better vanadium dispersion that lead to better catalytic properties above 350 degrees C, due to the presence of well dispersed V species partially incorporated into silica. The higher dichloromethane conversion achieved with both V-SBA-15 and V-SBA-15-i samples, as compared to MCF samples, are ascribed to longer residence times of both reactants and products within SBA-15 mesoporous channels, in contrast to three-dimensional MCF ultra large pores facilitating diffusion. Below 350 degrees C, both V-SBA-15-i and V-MCF-i samples showed higher dichloromethane conversion, basically due to the presence of micro-crystalline V(2)O(5) formed at the external surface of both materials. (C) 2010 Elsevier B.V. All rights reserved.