1,1＇-Bisnaphthol　(BINOL)　has　been　successfully　identified　as　a　new　organic　photocatalyst　framework　for　metal-free　atom　transfer　radical　polymerization　(ATRP),　and　good　control　over　the　molecular　weight,　narrow　dispersity　and　high　chain-end　fidelity　is　achieved　under　visible　light　mediation.　The　BINOL　framework　shows　high　modifiability,　which　enables　the　tuning　of　its　photophysical　properties　by　introducing　different　substituents　at　the　3,3＇-positions　of　BINOL　to　realize　controlled/living　polymerization.　©　2019　The　Royal　Society　of　Chemistry.