A Fenton-like catalyst prepared from tetrabutylammonium chloride and ferric trichloride was characterized by Fourier transform infrared, UV-vis and Raman spectroscopy. The catalyst (C4H9)(4)NFeCl4 (TBAFeCl(4)) in an extraction and catalytic oxidative desulfurization (ECODS) system containing H2O2 and the ionic liquid (IL) 1-decyl-3-methylimidazolium tetrafluoroborate ([Dmim]BF4) exhibited high catalytic activity for the removal of dibenzothiophene (DBT) in model diesel. Desulfurization with the Fenton-like catalyst TBAFeCl(4) in ECODS involves the structural distortion of DBT via polarization of the IL and its subsequent oxidation. The catalytic system could be recycled multiple times without significant decrease in desulfurization activity due to the high stability of the system.