A novel hybrid Anderson-type polyoxometalate, {[(CH3)(3)N(CH2)(2)OH](2)}[H0.2K0.2Na2.6(H2O)(6)][IMO6O24] (Abbreviated as (ChO)(2)K0.2Na2.6IMo6) was synthesized in a deep eutectic solvent and characterized by XRD, FT-IR, thermal analysis, electrochemical measurements and inductively-coupled plasma, atomic emission spectrometer (ICP-AES). This hybrid polyoxometalate was used as a catalyst in ionic liquids (ILs) for desulfurization of model diesel. The catalyst (ChO)(2)K0.2Na2.6IMo6 in the extraction and catalytic oxidative desulfurization (ECODS) system, containing H2O2 and 1-octyl-3-methylimidazolium tetrafluoroborate (OmimBF(4)), displayed so high activity that the removal of DBT can reach 100% at 60 degrees C in 60 min. Sulfur removal for S-compounds was in the following order: DBT > 4,6-DMDBT > BT. The desulfurization system shows so good stability that it can be recycled 20 times without noticeable decrease in activity. (C) 2016 Elsevier B.V. All rights reserved.