For the first time, methyltrioxorhenium (MTO) is used as a catalyst for the extractive and catalytic oxidative desulfurization (ECODS) of model oil and fluid catalytic cracking (FCC) gasoline, with 30% H2O2 as the oxidant and ionic liquids as the solvent and extractant for the removal of organic sulfur at moderate temperatures (below 60 degrees C). The ECODS is highly efficient with low catalyst loading (1-5 mol %). The mono- and bisperoxorhenium compounds formed via the reactions of MTO and H2O2 are proven to be catalytic active species for the oxidation of organic sulfides, such as thioethers, thiophene, and alkyl thiophenes contained in the FCC gasoline. After the oxidation, the oxidized products were easily extracted into the ionic liquid phase from the oil phase. The sulfur removal can reach up to 99% for the model oil (with an initial sulfur content of 200 mu g/mL) and 91% of the Fushun FCC gasoline (with an initial sulfur content of ca. 142 mu g/mL) within 2 h under the optimized conditions. The octane number of the gasoline is reduced by only about 0.7, without significant changes in hydrocarbon group composition after desulfurization.