Living radical polymerizations of styrene were performed under emulsion atom transfer radical polymerization conditions with latexes prepared by a nanoprecipitation technique recently developed for the stable free-radical polymerization process. Latexes were prepared by the precipitation of a solution of low-molecular-weight Polystyrene in acetone into a solution of a surfactant in water. The resulting particles were swollen with styrene and then heated. The effects of various surfactants and hydrophobic ligands, the reaction temperature, and the ligand/copper(I) bromide ratio were studied. The best results were obtained with the nonionic surfactant Brij 98 in combination with the hydrophobic ligand N,N-bis(2-pyridylmethyl)octadecylamine and a ligand/copper(I) bromide ratio of 1.5 at a reaction temperature of 85-90 degrees C. Under these conditions, latexes with good colloidal stability with average particle diameters of 200 nm were obtained. The molecular weight distributions of the polystyrenes were narrow, although the experimental molecular weights were slightly larger than the theoretical ones because not all the macroinitiator appeared to reinitiate. (c) 2006 Wiley Periodicals, Inc.