Preparation of continuous silica gel in the presence of dissolved Cr(NO3)(3) leads to a hard high surface area (710 m(2)/g) microporous xerogel. Formation of the gel in the pore structure of mesoporous Pore-Expanded MCM-41 (PE-MCM-41) and macroporous commercial Cab-O-Sil silica results in retention of the mesoporous structure in the case of PE-MCM-41, and the formation of a powder with a broad pore size distribution in the case of Cab-O-Sil silica. Comparison of the catalytic activities in non-oxidative dehydrogenation of propane revealed a linear correlation of the initial conversion with the surface area for all three samples. The sample prepared from PE-MCM-41 through a sol-gel assisted procedure was the most active, particularly with respect to the catalysts prepared by simple wet impregnation with chromium nitrate.