The emulsion copolymerization of styrene and sodium acrylate is reported using either a water-soluble initiator (potassium persulfate, or KPS), or an oil-soluble one [2,2-azoisobutyronitrile (AIBN)]. Reaction rates are fast with both KPS and AIBN. With KPS, conversions ú90% are achieved in 50 min, with AIBN, conversions reach 85% in 100 min. Particle size, measured by quasielectric light scattering (QLS), increases with conversion. Particle size in final latices is Ç 70-80 nm. Copolymer formation is confirmed by infrared (IR) spectroscopy, plasma emission spectroscopy (PES), and scanning electron microscopy (SEM). IR and PES indicate that mainly sodium acrylate reacts at the beginning of the reaction and then styrene is incorporated in the copolymer backbone. The copolymer produced with KPS contains more sodium acrylate than the one made with AIBN. These differences can be explained in terms of the reactivities and partitioning (local concentrations) of the monomers and of the type of initiator used. Thermomechanical analysis (TMA) of the copolymers reveals two transitions: one at Ç 100ЊC, which is due to the glass transition temperature (T g ) of polystyrene blocky segments in the copolymer, and another one at higher temperatures, which is associated to the T g of segments composed of alternated sodium acrylate and styrene units. The higher-temperature transition shifts to lower values as the reaction proceeds because these segments become richer in styrene.