Acidic and cesium salts of polyoxometalate (POM) with and without vanadium supported on MCM-41 were synthesized and their catalytic activities were investigated in the oxidation of cyclohexane with H2O2 under solvent-free condition. The products are cyclohexanol and cyclohexanone. The catalytic activity order is: CsVPOM/MCM > HVPOM/MCM > CsPOM/MCM ~ HPOM/MCM > CsVPOM > CsPOM catalysts. High conversion and selectivity to cyclohexanone over the supported catalysts are due to redox property and high surface area. These heterogeneous catalysts can be reused.