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The transition metal salts (Cu2+, Co2+ and Ni2+) of 10-molybdo-2-vanadophosphoric acid (H5[PMo10V2O40]) were supported on hexagonal mesoporous silica (HMS), and the resultant materials were used as catalysts for the selective oxidation of propylene to acetone by molecular oxygen. CuH3[PMo10V2O40]/HMS showed a high selectivity for acetone of 84.2% at 17.8% propylene conversion in a tubular fixed-bed reactor system under atmospheric pressure at 423 K. The high yield of acetone over CuH3[PMo10V2O40]/HMS at 423 K resulted from the proper acidity and oxidation ability of the heteropoly compound, the nature (acid property, redox property, etc.) of the Cu2+ counter-ion, the high surface area of the HMS support and the proper reaction temperature for the propylene oxidation. [Copyright &y& Elsevier]