A novel surfactant active RAFT agent as a suriniferter, composed of dithiobenzoyl main structure and benzoic hydrophobic/carboxylate hydrophilic moiety, was synthesized and applied to living radical emulsion polymerization of poly(methyl methacrylate) (PMMA) initiated by UV irradiation in the absence of added surfactant and additional initiator at various temperatures. Stable spherical beads of PMMA were successfully obtained using the suriniferter, maintaining the living radical polymerization characteristics. The PDI varies from 1.21 to 1.43 and the final particle sizes vary from 407 to 304 nm with increase in polymerization temperature from 60 to 80 ℃. The ratio of the triad tacticity for syndiotactic, atactic, and isotactic configurations of the synthesized PMMA is 54.3, 38.6, and 7.1, respectively, and the glass transition temperature (T_g) is 126.6 ℃, which is much higher than that of the commercial PMMA (T_g = 105 ℃).