A new method to form colloidally stable oligosaccharide-grafted synthetic polymer particles has been developed. The oligosaccharides, of weight-average degree of polymerization similar to 38, were obtained by enzymatic debranching of amylopectin. Through the use of a cerium(IV)-based redox initiation process, oligosaccharide chains are grafted onto a synthetic polymer colloid comprising electrostatically stabilized poly(methyl methacrylate) or polystyrene latex particles swollen with methyl methacrylate monomer. Ce(IV) creates a radical species on these oligosaccharides, which then propagates, initially with aqueous-phase monomer, then with the methyl methacrylate monomer inside the particles. Ultracentrifugation, NMR, and total starch analyses together prove that the grafting process has occurred, with at least 7.7 wt % starch grafted and a grafting efficiency of 33%. The surfactant used in latex preparation was removed by dialysis, resulting in particles colloidally stabilized with only linear starch as a steric stabilizer. The debranched starch that comprises these oligosaccharides is found to be a remarkably effective colloidal stabilizer, albeit at low electrolyte concentration, stabilizing particles with very sparse surface coverage.