In this work, a photoinduced iron(III)-based atom transfer radical polymerization (ATRP) without any reducing agents and additional initiators was suggested. In addition, detailed kinetic studies, including the effects of ligand and catalyst concentrations on polymerization kinetics, and the polymerization behaviors using various solvents and monomer types were evaluated for this new polymerization technique. Results showed that photoinduced iron(III)-mediated ATRP using 5000 ppm catalyst loading with 1 equiv of ligand in N,N-dimethylformamide (DMF) produced poly(methyl methacrylate) with low molecular weight distribution (M-w/M-n < 1.45) and that the evolution of molecular weight (Mn) was linearly related to monomer conversion. 1HNMR analysis confirmed that the resulting polymer prepared through photoinduced ATRP in the present work was initiated by methyl 2,3-dichloroisobutyrate. Facile temporal control and the successful chain extension highlighted the good chain-end functionality of the resulting polymers. In short, this work provided a study on additional alkyl halides initiator-free ATRP and its application in the synthesis of methacrylate polymers with narrow M-w/M-n.