A series of terpolymers (HAS) with different molecular weights and copolymer ratios were synthesized from 5-hydroperoxy-5-methyl-1-hexene-3-yne, acrylic acid, and styrene. The composition of terpolymers was verified by means of iodometric and potentiometric methods. The critical micelle concentration of HAS was determined by surface tension measurements at the air-water interface. The emulsion polymerization of styrene was carried out using HAS as an inisurf (i.e., the molecule which combines the properties of initiator and surfactant). The effects of the terpolymer composition, concentration, and reaction temperature on the rate of polymerization and final particle size/number have been studied. It was found that the increase of the reaction temperature and the hydroperoxide monomer content in the terpolymer molecule results into a higher amount of small size particles. The final particles possess electrostatic and sterical stabilities due to the specific design of the HAS molecule. Thus, the obtained latexes showed an excellent stability against the addition of electrolytes and freeze-thaw cycles.