A B-type Anderson polyoxomolybdates with mixed-valence molybdenum ions, [(C18H37)(2)N(CH3)(2)](3)Co(OH)(6)(Mo6O18)-O-(V,VI), was prepared and characterized by Fourier transform infrared spectroscopy(FT-IR), UV-vis diffuse reflectance spectroscopy (UV-vis DRS), differential thermal analysis (DTA) and X-ray photoelectron spectrum (XPS). The polyoxometalate shows high catalytic activity in aerobic oxidative desulfurization of model diesel and the turnover number (TON) can reach about 4200 in absence of any sacrificial agent under mild conditions. The quaternary ammonium cations in the catalysts play a vital role in the aerobic oxidative desulfurization system. The catalytic activity for the oxidation of sulfur-containing compounds decreases in the order of 4,6-DMDBT > DBT > BT. (C) 2013 Elsevier B.V. All rights reserved.