The fluoride anion-ligated ferryloxo tetramesitylporphyrin pi cation radical compound, (TMP.+)(FeO)-O-IV=-(F) (1-F) [v(Fe=O-16) at 807 cm(-1) and v(Fe=O-18) at 771 cm(-1)] was generated by two different routes and structurally characterized by resonance Raman spectroscopy. The green compounds of Hashimoto et al. [v(Fe=O) Eit 828 cm(-1)] and Kincaid et al. [v(Fe=O) at 802 cm(-1)] were reassignd to 1-MeOH and l-Cl, respectively, based on this Raman spectrum and previously reported NMR data.