The controlled and target-specific release of CO to a target site upon photoactivation has recently emerged as a promising tool for targeted anticancer activity. However, the present CO-releasing molecules (CORMs) suffer several limitations, including poor delivery to the tumor site. In this study, we reported the synthesis, characterization, and caspase 3/7-dependent apoptosis (IC 50 : 232 μg ml −1 or 29.03 nM) in A549 cells by manganese(I) carbonylfunctionalized gold nanoparticles (1-AuNPs) on dual photosensitization in red light (600-720 nm, 30 J cm −2). The 1-AuNPs, however, remained nontoxic to A549 cells in the dark. The Mn(I)-CO complex (1) exhibited photocytotoxicity (IC 50 : 38.1 μM in red light; IC 50 : 88 μM in dark) as well. Dual photosensitization with red light leading to rapid, synergic CO release and singlet oxygen (1 O 2) generation were the principal mechanism for the photocytotoxicity, which was studied in detail. Photoactivated CO release resulted in TURN-ON luminescence in A549 cells and renders the hybrid 1-AuNPs an ideal, nextgeneration nanotheranostic agent. K E Y W O R D S "TURN-ON" fluorescence in vitro on photo-induced CO release, dual photosensitization, manganese(I) carbonyl-functionalized gold nanoparticles, red light-induced CO release and singlet oxygen (1 O 2) generation, remarkable photocytotoxicity in red light