A novel method for synthesis of substituted μ-oxo-bis[tetraphenyl porphyrinatoiron] compounds ([TRPPFe]2O) based on the reaction among free base porphyrins (TRPPH2), FeSO4·7H2O and H2O in one pot was proposed and investigated. Four kinds of [TRPPFe]2O were synthesized by this novel synthetic method, and their structures were characterized by elemental analysis, infrared spectra and UV-vis spectroscopy. The reaction conditions, including the effect of different iron salts on the formation of [TRPPFe]2O, the reaction time between FeSO4·7H2O and TRPPH2, the molar ratio of FeSO4·7H2O/TRPPH2 as well as the volume ratio of H2O/DMF, were investigated. The [TRPPFe]2O yield of 93%-98% could be obtained under the following optimal conditions: the reaction time of FeSO4·7H2O with TRPPH2 was about 10 h, the molar ratio of FeSO4·7H2O/TRPPH2 about 5︰1, and the volume ra-tio of H2O/DMF exceeded 2︰1. Further research indicated that only TRPPFeCl were formed once FeSO4·7H2O was replaced by FeCl2·4H2O, the reason of which might be that halogen ions in iron salts interfered the formation of [TRPPFe]2O, suggesting that halogen ions should be avoided in this novel synthetic method. A novel method for synthesis of substituted μ-oxo-bis [tetraphenyl porphyrinatoiron] compounds ([TRPPFe] 2O) based on the reaction among free base porphyrins (TRPPH2), FeSO4 · 7H2O and H2O in one pot was proposed and investigated. of [TRPPFe] 2O were synthesized by this novel synthetic method, and their structures were characterized by elemental analysis, infrared spectra and UV-vis spectroscopy. The reaction conditions, including the effect of different iron salts on the formation of [TRPPFe] 2O, the reaction time between FeSO4 · 7H2O and TRPPH2, the molar ratio of FeSO4 · 7H2O / TRPPH2 as well as the volume ratio of H2O / DMF, were investigated. The [TRPPFe] 2O yield of 93% -98% could be obtained under the the following optimal conditions: the reaction time of FeSO4 · 7H2O with TRPPH2 was about 10 h, the molar ratio of FeSO4 · 7H2O / TRPPH2 about 5: 1, and the volume ra- tio of H2O / DMF exceeded 2 ︰ 1. Further research indicated that only TRPPFeCl were formed once FeSO4 · 7H2O was replaced by F eCl2 · 4H2O, the reason of which might be that halogen ions in iron salts interfered the formation of [TRPPFe] 2O, suggesting that the halogen ions should be avoided in this novel synthetic method.