High-valent iron-oxo intermediates play central roles as active oxidants in enzymatic and synthetic catalytic oxidations. Many transition metal catalysts are designed for biomimetic studies of the predominant oxidation catalysts in Nature, the cytochrome P450 enzymes. In this work, a new photochemical method to generate high-valent iron-oxo porphyrin models was discovered. As controlled by the electronic nature of porphyrin ligands, iron(IV)-oxo porphyrin radical cations (Compound I model) and iron(IV)-oxo porphyrin derivatives (Compound II model) were produced. These observations indicate that the photochemical reactions involve a heterolytic cleavage of O-Br in precursors to give a putative iron(V)-oxo intermediate, which might relax to Compound I through electron transfer from porphyrin to the iron or undergo rapid comproportionation reaction with residual iron(III) to afford the Compound II derivative. Furthermore, visible light photolysis of bis-porphyrins-dimanganese(III)-μ-oxo complexes, [MnIII(Por)]2O, was studied in three porphyrin systems. Direct conversion of manganese(III)-μ-oxo dimers to manganese(IV)-oxo porphyrins [MnIV(Por)(O)] and manganese(III) products was observed in benzene solution upon light irradiation. The spectral signature of [MnIV(Por)(O)] was further confirmed by production of the same species in the reported reaction of the [MnIII(Por)Cl] with PhI(OAc)2. Continuous irradiation of bis-porphyrins-dimanganese(III)-μ-oxo complexes in the presence of pyridine or triphenylphospine gave rise to the formation of [MnII(Por)(Py)] or [MnII(Por)(PPh3)], which are stable to be detected. A photo-disproportionation mechanism similar to that for bis-porphyrins-diiron(III)-μ-oxo complex was proposed to explain above photochemical behaviors of bis-porphyrins-dimanganese(III)-μ-oxo complexes. With iodobenzene diacetate [PhI(OAc)2] as the oxygen source, manganese(III) porphyrin complexes exhibit remarkable catalytic activity towards the selective oxidation of alkenes and activated hydrocarbons. Conspicuous is the fact that the readily soluble PhI(OAc)2 in the presence of a small amount of water is more efficient oxygen source than the commonly used PhIO under same conditions. High selectivity for epoxides and excellent catalytic efficiency with up to 10,000 Turnovers (TONs) were achieved in alkene epoxidations. A manganese(IV)-oxo porphyrin was observed in the oxidation of the manganese(III) porphyrin and PhI(OAc)2. However, catalytic competition and Hammett studies suggested that the more reactive manganese(V)-oxo intermediate was favored as the premier active oxidant, even it is too short-lived to be detected in the catalytic reaction.