Using sodium tungstate﹑cobalt acetate and stannic chloride as raw materials, Sn-substituted heteropoly acid potassium salt K7MⅡW11SnⅣO39OH (M =Co,Fe,Ni,Zn,Mn) and quaternary ammonium salt were synthesized by the acidification method, and characterized by Fourier transform infrared (FTIR), X-ray diffraction (XRD) and Inductively Coupled Plasma-Atomic Emission Spectrometry(ICP-AES). Its catalytic activity was measured in the oxidation of cyclohexanol to cyclohexanone with mass fraction 30% aqueous hydrogen peroxide as an oxidant. The conversion of cyclohexanol and the selectivity of cyclohexanone were found to be as high as 95.68% and 96.75% under the optimum conditions which the quantity of catalyst (C4H9)4NHxCoⅡW11SnⅣ was 0.25mmol, cyclohexanol was 0.05 mol, hydrogen peroxide was 0.2 mol, acetonitrile was 0.2 mol at 85℃for 2 h, and a possible reaction mechanism of the oxidation of cyclohexanol was concluded that transition metal Sn was act as catalytic active center.