The electronic structures, and, particularly, the nature of the HOMO in a series of the low-spin PcFeL₂, PcFeL′L″, and [PcFeX₂]^2- iron(II) phthalocyanine complexes were probed by electrochemical, spectroelectrochemical and chemical oxidation approaches and complimented by MCD spectroscopy as well as theoretical (DFT and TDDFT) studies. In general, energies of the metal-centered occupied orbitals in the various six-coordinate iron phthalocyanine complexes correlate well with Lever’s electrochemical parameter, E_L, and intercross the phthalocyanine-centered a_1u orbital in several compounds with moderate-to-strong p-accepting axial ligands. In these cases, an oxidation of the phthalocyanine macrocycle (Pc(2-)/Pc(1-)) rather than the central metal ion (Fe(II)/Fe(III)) was theoretically predicted and experimentally confirmed. The experimentally derived using MCD spectroscopy or theoretically predicted using TDDFT calculations energy of the MLCT1 transition (d_π→Pc(π*)) on iron(II) phthalocyanines also follows the trend expected for the E_L properties of the axial ligands.