Grafting of Acrylonitrile(AN) onto water soluble polymers like Polyvinyl alcohol(PVA), was carried in the presence of Ag(I) using Ce(IV) as an initiator in H2SO4 medium at 313K .The rate of oxidation (Roxi) was determined for catalysed and uncatalysed oxidation. The rate of grafting (Rg) and grafting efficiency(GE) were determined for [Ag(I)] catalysis. The rate of grafting was found to increase with increase in [PVA], [AN] and [Ag(I)] and the orders were 0.72, 1.43 and 0.41 respectively.. A probable mechanism involving the formation of Ag(I) - polymer adduct followed by its oxidation with Ce(IV) to Ag(II) - polymer adduct which decomposes to give initiating radicals is proposed to explain the results.