The position of the experimentally observed (in the UV-vis and magnetic circular dichroism (MCD) spectra) low-energy metal-to-ligand charge-transfer (MLCT) band in low-spin iron(II) phthalocyanine complexes of general formula PcFeL2, PcFeL'L″, and [PcFeX2]2- (L, L', or L″ are neutral and X- is an anionic axial ligand) was correlated with the Lever's electrochemical EL scale values for the axial ligands. The time-dependent density functional theory (TDDFT)-predicted UV-vis spectra are in very good agreement with the experimental data for all complexes. In the majority of compounds, TDDFT predicts that the first degenerate MLCT band that correlates with the MCD A-term observed between 360 and 480 nm is dominated by an eg (Fe, dπ) → b1u (Pc, π*) single-electron excitation (in traditional D4h point group notation) and agrees well with the previous assignment discussed by Stillman and co-workers[ Inorg. Chem. 1994, 33, 573-583]. The TDDFT calculations also suggest a small energy gap for b1u/b2u (Pc, π*) orbital splitting and closeness of the MLCT1 eg (Fe, dπ) → b1u (Pc, π*) and MLCT2 eg (Fe, dπ) → b2u (Pc, π*) transitions. In the case of the PcFeL2 complexes with phosphines as the axial ligands, additional degenerate charge-transfer transitions were observed between 450 and 500 nm. These transitions are dominated by a2u (Pc + L, π) → eg (Pc, π*) single-electron excitations and are unique for the PcFe(PR3)2 complexes. The energy of the phthalocyanine-based a2u orbital has large axial ligand dependency and is the reason for a large energy deviation for B1 a2u (Pc + L, π) → eg (Pc, π*) transition. The energies of the axial ligand-to-iron, axial ligand-to-phthalocyanine, iron-to-axial ligand, and phthalocyanine-to-axial ligand charge-transfer transitions were discussed on the basis of TDDFT calculations.