A novel vanadium polyoxometalate [(C6H5CH2)(CH3)3N]3[H3V10O28]3H2O works as a useful oxidant for selective and rapid oxidation of benzylic alcohols to the corresponding carbonyl compounds in the presence of PTSA under solvent-free, room temperature conditions in excellent yield. The same vanadium polyoxometalate can be applied for the oxidative transformation of variety of aldoxime and ketoxime to the corresponding aldehydes and ketones under solvent less condition at room temperature within a minute. Moreover this vanadium polyoxometalate works as a useful oxidant for the oxidation of thiols to disulfldes in water under mild reaction conditions in an excellent yield.