A method is presented for synthesizing surfactant-free latexes comprising starch-graft-(vinyl polymer) starting with a suspension of amylopectin, either native or modified, then using cerium(IV) with either potassium persulfate or glucose to create grafting sites on the starch. Latex particles comprising polystyrene, poly(styrene-co-(n-butyl acrylate)) and poly(vinyl acetate) grafted onto high molecular weight amylopectin were developed, with up to 80% of the starch effectively grafted to the particles. These latexes were colloidally stable against electrolyte (several months in 4 M NaCl). Reaction rates of Ce4+ with simple sugars and polysaccharides were investigated, as well as the gelation mechanism of the latex. (c) 2007 Wiley Periodicals, Inc.