A method is developed for anchoring enzymatically degraded cationized starch as electrosteric stabilizers onto synthetic latices, using cerium(IV) to create free-radical grafting sites on the starch. Direct anchoring of debranched starch onto a poly (methyl methacrylate) seed latex yields a latex stabilized by well-defined oligosaccharides. Using a-amylase to randomly cleave starch to form (1 -> 4)-alpha-glucans, and a comonomer, N-isopropyl acrylamide (NIPAM), whose corresponding polymer exhibits a lower critical solution temperature (LCST), creates a means to synthesize block (or graft) oligomers of oligosaccharide and synthetic polymer, which are water soluble at room temperature. Above 30 degrees C, they become amphiphilic and form self-emulsifying nanoparticles (sometimes termed "frozen micelles") from which a synthetic latex is grown after addition of methyl methacrylate, the collapsed NIPAM-containing entities functioning as a type of in situ seed. This synthesis of stable synthetic latex particles is shown to have a high grafting efficiency. The starch fragments were characterized by H-1 solution-state NMR before grafting, and C-13 solid-state cross-polarization magic-angle spinning (CP-MAS) NMR was used to characterize the starch oligomers actually grafted on the final latex. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1836-1852, 2009