High-spin (hs) ferric heme centers occur in the catalytic or redox cycles of many metalloproteins and exhibit very complicated magnetic circular dichroism (MCD) and UV-vis absorption, spectra. Therefore, detailed assignments of the MCD spectra of these species are missing. In this study, the electronic spectra (MCD and UV-vis) of the five-coordinate hs ferric model complex [Fe(TPP)(Cl)] are analyzed and assigned for the first time, A correlated fit of the absorption and low-temperature MCD spectra of [Fe(TPP)(Cl)] lead to the identification of at least 20 different electronic transitions. The assignments of these spectra are based on the following: (a) variable temperature and variable field saturation data, (b) time-dependent density functional theory calculations, (c) MCD pseudo A-terms, and (d) correlation to resonance Raman (rRaman) data to validate the assignments. From these results, a number of puzzling questions about the electronic spectra of [Fe(TPP)(Cl)] are answered. The Soret band in [Fe(TPP)(Cl)] is split into three components because one of its components is mixed with the porphyrin A(2u)< 72 > -> Eg < 82/83 > (pi -> pi*) transition. The broad, intense absorption feature at higher energy from the Soret band is due to one of the Soret components and a mixed or and a chloro to iron CT transition. The high-temperature MCD data allow for the identification of the Q(v) band at 20 202 cm(-1), which corresponds to the C-term feature at 20 150 cm(-1). Q is not observed but can be localized by correlation to rRaman data published before. Finally, the low energy absorption band around 650 nm is assigned to two P -> Fe charge transfer transitions, one being the long sought after A(1u)(HOMO) -> d(pi) transition.