Acidic ionic liquids (ILs) have been employed as extractant and catalyst in the oxidative desulfurization (ODS) process of fuels in recent years. Several Lewisacidic ionic liquids [C63MPy]Cl/nFeCl3 (molar fraction n = 0.5, 1, 2, 3) and [C6MIM]Cl/FeCl3 were prepared and used to remove the aromatic sulfur compounds dibenzothiophene and benzothiophene from fuels. In the ODS process, the used ILs acted as both extractant and catalyst with 30 wt% hydrogen peroxide aqueous solution as oxidant. The effects of Lewis acidity of ILs, IL's cation structure, molar ratio of O/S, reaction temperature, and different sulfur compounds on the sulfur removal of model oil were investigated. The results indicated that the sulfur removal for dibenzothiophene was affected by Lewis acidity of ILs and nearly reached 100% by [C63MPy]Cl/FeCl3 at conditions of 298K, IL/oil mass ratio of 1/3, O/S molar ratio of 4/1, in 20 min. The sulfur removal of real gasoline reached 99.7% after seven ODS runs in the [C63MPy]Cl/FeCl3-H2O2 system.