A phthalocyanine (Pc) initiator, tetrakis(2-bromopropyloxyester)ethylthiophthalocyaninatozinc(II) (ZnPc-Br), was prepared and successfully applied to atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) for the first time. Bromine end groups of the synthesized Pc took part in the initiation of the MMA chain growth. Polymerization was demonstrated by monomodal molecular weight distribution of the synthesized polymers and their increasing molecular weight behavior with reaction time. UV-Vis absorption, fluorescence, and transmittance properties of the polymers were also examined. The results indicate that the ZnPc-Br-based initiator is potentially applicable in ATRP applied to MMA in order to obtain and develop functional acrylic materials.