We have successfully synthesized and characterized a new low-spin iron(III) bis(4-cyanopyridine) complex with a meso-porphyrin substituted in the para positions of the phenyls by the methoxy group, namely the bis(4-cyanopyridine)[(meso-tetrakis(4-metoxyphenylporphyrinato)]iron(III) trifluoromethanesulfonate chlorobenzene monosolvate complex with the formula [FeIII(TMPP)(4-CNpy)2]SO3CF3.C6H5Cl (I). This species was characterized through ultraviolet–visible, Fourier-transform infrared and Mössbauer spectroscopy as well as by SQUID magnetometry, cyclic voltammetry, and X-ray crystallography. These characterizations indicated that our synthetic heme model is a low-spin (S = 1/2) coordination compound and especially shows that the structural, electronic and the magnetic properties of complex (I) are closely dominated by the presence of the methoxy σ-donor group at the para positions of the meso-porphyrin.