The influence of electronic and structural effects in FeCl4 and FeCl6 entities has been investigated through X-ray absorption spectroscopy and theoretical calculations of electronic transition energies using the MS-LSD method. The relative importance of the formal oxidation degree of the metal, the metal-ligand distance, and the symmetry of the site on the energy of near-edge structures are studied. The principal effect is the stabilization of the iron Is orbital in the ground state when the oxidation degree increases. The accuracy of the theoretical determination regarding the experimental spectra is discussed. The incidence of the same electronic parameters on the intensities of near-edge structures is also investigated through a transition cross section calculation.