Graft copolymerization of methyl methacrylate onto PVC was carried out using Ce(IV)-glucose redox system in aqueous sulfuric acid medium under nitrogen atmosphere. To find out the optimum conditions for grafting, effects of concentrations of metal ion, glucose, monomer, and acid on the percentage of grafting was studied. The graft yield was found to be influenced by reaction time, temperature, and amount of PVC. An appreciably high graft yield could be achieved with the present system. On the basis of the results from the present study, a plausible reaction mechanism has been proposed.