Abstract: Sandwich-type polytangstozincic quaternary ammonium salts Q12[WZn3(H2O)2(ZnW9O34)2](Q=[C18H37(CH3)3N]+, [C16H33(CH3)3N]+, and [C12H25(CH3)3N]+) were successfully synthesized, and the composite catalyst of mixed surfactant and the salts were made and characterized by X-ray diffraction, Fourier transform infrared spectroscopy, thermal gravity analysis, and elemental analysis. Using mixture of dibenzothiphene, a model compound and hydrogen peroxide, an oxidant as test feed, the as-synthesized composite materials were applied to the catalytic oxidative desulfurization of the mixture to evaluate their activity. The results show that the desulfurization rate of dibenzothiphene is enhanced with increasing alkyl chain length of the surfactant. At 60 °C for 2 h, the S removal rate reaches up to 94.4%.