The thermally initiated emulsion copolymerization of styrene (ST) and methyl methacrylate (MMA) was carried out in the absence of conventional initiators. The hydroperoxide (HPO) concentration in the monomers, sodium dodecyl sulfate (SDS), deionized water, and the formulation of those for emulsion copolymerization were measured. The HPO concentration in ST and MMA increased with the storage time, and were considered to be the major sources of HPO. The thermal decomposition of hydroperoxide in monomers, the thermal initiation of ST by Mayo mechanism, and the complex formation between SDS and the monomers were proposed to be three main sources of the radical generation. It was confirmed that new polymer particles were generated throughout the polymerization process, and consequently resulted in a broader distribution of polymer particle size, compared with that for conventional emulsion polymerization. Approximately 80 wt % of monomer conversion was obtained in the presence of SDS at 373 K in 24 h. The initiation rate of the 30 wt % monomer charge was faster than those of 10 wt % and 20 wt % monomer charge. The latex instability at higher solid content was improved by adding electrolyte to promote the electrostatic repulsion force between the polymer particles.