A vibrational resonance Raman effect of the totally symmetric Fe - F stretching mode at 453 cm^−1^is observed for high-spin tetra-n-butylammonium di(fluoro)tetraphenylporphyrinatoferrate(III). Typical A-term scattering with a high intensity overtone progression is proposed to be due to coincidence of the excitation energy with a ‘trip-sextet’ transition at 21 000 cm^−1^. The complex salt crystallizes as a dichloromethane solvate in the monoclinic space group P12/n1 (No. 13): a = 12.287(3) Å, b = 12.381(4) Å, c = 20.761(5) Å,β = 105.05(2)°,Z = 4. The iron atom is in the centre of the slightly distorted porphyrinate core. The Fe - F distance is 1.907(2) Å, the averaged Fe - N~p~distance 2.072(2) Å. There is no hydrogen bonding of the floride ligand to the cation or solvate. Contrary to the high-spin difluoro complex, a molecular electronic resonance Raman effect is detected for low-spin pyridine(cyano)- and -(thiocyanato( N )tetraphenylporphyrinatoiron(III) at 550 and 561/578 cm^−1^respectively. This Γ~7 g~→Γ~8 g~transition is a consequence of the spin-orbit splitting of the^2^T~2 g~ground state of low-spin Fe^III^assuming octahedral symmetry. B-term scattering is active by excitation with 476.5 nm, effectively enhancing the intensity of non-totally symmetric electronic and vibrational transitions.