In this manuscript, phosphotungestovanadate (N(tBu)(4))(4)HPW10V2O40 (PWV) as a Keggin-type polyoxometalate was synthesized and immobilized on polyvinyl alcohol (PVA) via sol gel method. The materials characterized by FT-IR, XRD, UV-vis, SEM and P-31 NMR spectroscopy. Catalytic activity of synthesized nanocomposite was tested on oxidative desulphurization of actual gasoline and results are compared with that of model sulphur compounds. This Keggin-type supported catalyst was shown to be able to have oxidative desulphurization of model sulphur compounds and actual gasoline with high yield. The addition of acetic acid enhanced the conversion. The advantages of this method lie in its mild condition, low cost, large scale, simplicity and environmentally friendly route. (C) 2015 Elsevier B.V. All rights reserved.