Two manganese(V)-oxo corroles [Mn(Cor)O] that differ in their electronic environments were produced by visible light irradiation of highly photo-labile corrole-manganese(IV) bromates. The corrole ligands under study include 5,10,15-tris(pentafluorophenyl)corrole (TPFC), and 5,10,15-triphenylcorrole (TPC). The kinetics of oxygen transfer atom (OAT) reactions with various organic reductants by these photo-generated Mn(Cor)O were also studied in CHCN and CHCl solutions. Mn(Cor)O exhibits remarkable solvent and ligand effect on its reactivity and spectral behavior. In the more electron-deficient TPFC system and in the polar solvent CHCN, Mn(Cor)O returned Mn corrole in the end of oxidation reactions. However, in the less polar solvent CHCl or in the less electron-deficient TPC system, Mn product was formed instead of Mn. Furthermore, with the same substrates and in the same solvent, the order of reactivity of Mn(Cor)O was TPC>TPFC, which is inverted from that expected based on the electron-demand of corrole ligands. Our spectral and kinetic results in this study provide compelling evidence in favor of multiple oxidation pathways, where Mn(Cor)O may serve as direct two-electron oxidant or undergo a disproportionation reaction to form a manganese(VI)-oxo corrole as the true oxidant. The choice of pathways is strongly dependent on the nature of the solvent and the corrole ligand.