Graft copolymerization of vinyl compounds onto chitin was studied, and an efficient and reproducible procedure has been established, cerium (IV) being used as the initiator. The reactions with acrylamide and acrylic acid onto powdery chitin were carried out under various conditions to elucidate the polymerization behavior in terms of grafting percentage. The amount of cerium (IV) affected the polymerization most strikingly, and grafting percentages showed maxima with suitable amounts of initiator for both the monomers. As a solvent water proved to be superior to aqueous nitric acid except the reaction with a small amount of initiator. Under appropriate conditions, around 240 and 200% grafting percentages were achieved for acrylamide and acrylic acid, respectively. The resulting graft copolymers showed much improved affinity for solvents and hygroscopicity compared to the original chitin.