Starch-polyacrylonitrile graft copolymers prepared in a number of aqueous-organic solvent systems with ceric ammonium nitrate as the initiator had more grafted chains than those prepared in water alone, and these were of lower molecular weight. Substitution of methanol for 80% of the water produced grafted chains with a molecular weight of 15,700 and a grafting frequency of 253 anhydroglucose units per graft. The influence of catalyst concentration, increased reaction temperature, and sodium sulfate on the composition of the copolymer were investigated for the methanol-water system.