AbstractGraft copolymers were prepared by the radical‐initiated polymerization of methyl methacrylate in aqueous slurries of granular corn starch. High conversions of monomer were realized, giving products which were readily recovered by filtration. The products were free‐flowing, white powders, which by microscopic examination looked much like granular starch. Grafting was demonstrated by extracting the granular products with ethylene dichloride, which in most instances removed only a minor part of the poly(methyl methacrylate). When azoisobutyronitrile was used for initiation, a high conversion of monomer resulted, but about 90% of the polymer was extractable with ethylene dichloride. Further evidence for grafting was obtained by extraction of predissolved product, prepared by dissolving the granular product in dimethyl sulfoxide, to destroy the structure of the starch granules, and precipitating with alcohol. The fractions soluble in ethylene dichloride contained significant amounts of carbohydrate. Similar treatment of product prepared with azoisobutyronitrile initiation or of physical blends of starch and poly(methyl methacrylate) gave much more efficient separation of starch from PMMA. Failure to obtain grafting with AIBN initiation suggests that grafting occurs mainly as a result of attack on starch by radicals generated by the reaction of hydrogen peroxide or organic hydroperoxide with ferrous iron. Acid hydrolysis of the products removed the starch. The PMMA so recovered typically had viscosity‐average molecular weights of the order of 106, which suggests the grafts contained very long branch chains of PMMA attached at very infrequent intervals.