The　orthogonality　of　different　types　of　living　polymerizations　allows　the　synthesis　of　polymers　with　diverse　compositions　and　functions.　However,　two　or　more　catalysts　are　normally　required　to　promote　the　integrated　polymerizations　separately,　and　few　could　deliver　a　photocontrol　on　both　polymerizations.　Herein,　we　demonstrate　that　BINOL　(1,1′-bi-2-naphthol)　with　appropriate　modification　can　be　evolved　into　a　type　of　dual-function　photocatalyst　that　can　exhibit　both　photoredox　and　photoacid　catalytic　activity　at　the　same　time.　This　dual　photofunction　could　enable　BINOLs　to　catalyze　the　metal-free　atom　transfer　radical　polymerization　and　ring-opening　polymerization　with　simultaneous　light　regulation.　The　utility　of　this　orthogonal　method　is　further　demonstrated　in　the　one-pot　synthesis　of　PMMA-b-PVL　block　copolymers　with　good　control　on　both　molecular　weight　and　low　dispersity.　©　2024　American　Chemical　Society.