A new polymer-bound peroxotungstate(VI) catalyst of the type [W(O)(2)(O-2)(CN)(2)]-PAN [PAN poly(acrylonitrile)] (PANW) has been prepared by reacting H2WO4 with 30% H2O2 and the macromolecular ligand, PAN at pH 5.0. The compound was characterized by elemental analysis, SEM, EDX, TGA and spectral studies (FTIR and C-13 NMR). Clean conversion of a variety of sulfides and dibenzothiophene (DBT) to the corresponding sulfoxide or sulfone, using H2O2 as oxidant, could be achieved in the presence of the heterogeneous catalyst PANW, by a versatile variation of reaction conditions. The reactions proceed under mild conditions to afford the resulting products with impressive turn over frequency (TOF). The catalyst exhibit complete chemoselectivity toward sulfur group of substituted sulfides with other oxidation prone functional groups. Easy regeneration and reusability of the catalyst for at least up to seven catalytic cycles with consistent activity and selectivity is an important attribute of the catalyst. (C) 2012 Elsevier B.V. All rights reserved.