Photosensitive alkoxyamine 2,2,6,6-tetramethyl-1-(1-phenylethoxy)piperidin-4-yl quinoline-2-carboxylate (PE-TEMPO-Q) was synthesized. Photochemical properties of PE-TEMPO-Q were studied to develop photoinduced nitroxide-mediated polymerization of methyl methacrylate (MMA). Rapid and facile polymerization at ambient temperature with PE-TEMPO-Q as an initiator was confirmed to proceed in a controlled mechanism based on the linear growth in molecular weight combined with relative narrow polydispersity index (1.4-1.8) of the resulting polymers. The stereochemistry of obtained polymers was also investigated, and the syndiotacticity slightly increased compared with the typical photopolymerization. Dual-controlled photopolymerization of MMA was achieved in the presence of synthesized alkoxyamine.