Abstract: Aiming at deep desulfurization of the gasoline, three amphiphilic catalysts [C18H37N(CH3)3]3+x [PMo12-xVxO40](x=1,2,3) were prepared and characterized. The amphiphilic vanadium (V)-substituted polyoxometalates were dissolved in water-immiscible ionic liquid ([Bmim]PF6) forming a H2O2-in-[Bmim]PF6 emulsion desulfurization system with 30 wt % H2O2 as oxidant. The catalytic oxidation of sulfur-containing model oil has been studied in detail under various reaction conditions using this system. The ionic liquid emulsion system showed high catalytic oxidative activity in the treatment of actual gasoline. Moreover, the mechanism of catalytic oxidation desulfurization was also elaborated.