A novel method for the synthesis of -oxo-bis[tetraarylporphyrinatoiron] ([TRPPFe] O) based on the reaction between tetraarylporphyrinironchloride (TRPPFeCl) and H O in toluene was investigated in this paper. Three kinds of [TRPPFe] O were synthesized by this novel synthetic method, and their structures were characterized by elemental analysis, IR spectra and UV-Vis spectroscopy.