Abstract In this research, a novel organic photocatalyst of 10-(Perylene-3-yl-10H-Phenoxazine (PHP) has been synthesized successfully from perylene and phenoxazine via Buchwald-Hartwig C-N coupling. The chemical structure of catalyst was determined via proton nuclear magnetic resonance (1H-NMR) spectrum and optical properties were investigated through UV-Vis spectroscopy. The PHP has been used as the reducing photoredox catalyst for organocatalyzed atom transfer radical polymerization (ATRP) under UV irradiation. The well controlled molecular weight of polymers based on methyl methacrylate monomers have been obtained with monomer conversion up to 77.61% and low polydispersity index under 1.5.