Organocatalytic　atom　transfer　radical　polymerization　(O-ATRP)　is　emerging　as　a　powerful　tool　for　the　synthesis　of　well-defined,　metal-free　polymers,　with　additional　spatiotemporal　control　by　light.　Herein,　based　on　the　design　logic　of　heteroatom-doping　of　polycyclic　arenes　for　photocatalyst　development,　a　series　of　chalcogenide　atom　(e.g.,　O,　S,　Se,　Te)-doped　anthracenes　as　potential　photocatalysts　for　O-ATRP　is　explored.　It　is　found　that　these　heteroatoms　have　a　significant　effect　on　the　photophysical　and　photoredox　properties,　leading　to　different　performance　in　the　O-ATRP　of　methyl　methacrylate　(MMA).　Upon　further　optimization,　the　selenium　analogues　of　N-aryl　phenothiazines　are　successfully　identified　as　effective　photocatalysts　for　O-ATRP,　which　can　promote　a　controlled　radical　polymerization　of　MMA.　©　2022　Wiley-VCH　GmbH.