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Phosphorus(V) trimethoxyl A 2 B triaryl corrole (2-P) with excellent optical characteristics induced cancer cells apoptosis upon light irradiation at 625 nm. [Display omitted] • Ga(III) and P(V) trimethoxyl A 2 B triaryl corrole were synthesized and characterized. • P(V) m , m' , p -trimethoxyl A 2 B triaryl corrole exhibited high singlet oxygen quantum yield, photostability, and excellent photodynamic activity against cancer cells. • P(V) m , mʼ , p -trimethoxyl A 2 B triaryl corrole photodynamic therapy treatment might cause tumor cells arrest at the sub-G1 phase and induced apoptosis triggered by ROS increasing upon light irradiation. Two new trimethoxyl A 2 B triaryl corroles 10-(2,4,6-trimethoxyphenyl)-5,15-bis(pentafluorophenyl)- corrole (1) and 10-(3,4,5-trimethoxyphenyl)-5,15-bis(pentafluorophenyl)-corrole (2) and their gallium(III) and phosphorus(V) (1-Ga , 1-P , 2-Ga and 2-P) complexes had been prepared and well characterized by UV–vis, NMR and HR-MS. Among all compounds, 2-Ga , 1-P and 2-P showed excellent in vivo photodynamic activity against the MDA-MB-231, A549, Hela and HepG2 cell lines upon light irradiation at 625 nm. And 2-P even exhibited higher phototoxicity than the clinical photosensitizer temoporfin. Also, 2-P exhibited the highest singlet oxygen quantum yield and photostability. The preliminary investigation revealed that 2-P could be rapidly absorbed by tumor cells and mainly located in the cytoplasm. After photodynamic therapy (PDT) treatment with 2-P , mitochondrial membrane potential destruction, intracellular ROS level increasing and nuclear fragmentation of cancer cells could be observed. Cell cycle analysis demonstrated that the 2-P PDT may cause tumor cell arrest at sub-G1 stage and induce early and late apoptosis of cells. These results suggest that 2-P is a promising candidate as a photosensitizer for photodynamic therapy. [ABSTRACT FROM AUTHOR]