Compound ([FeTPPbipy](•))n (TPP = meso-tetraphenylporphyrin and bipy = 4,4'-bipyridine) is the first example of a Fe-TPP-bipy coordination network, and it consists of 1D polymers packed through face-to-face and edge-to-face π-π interactions. The compound has been investigated by means of X-ray diffraction, IR, Mössbauer, UV-visible, and EPR spectroscopies, thermogravimetry, magnetic susceptibility measurements, and quantum-mechanical density functional theory (DFT) and time-dependent DFT calculations. The chemical formula for this compound can be confusing because it is compatible with Fe(II) and TPP(2-) anions. However, the spectroscopic and magnetic properties of this compound are consistent with the presence of low-spin Fe(III) ions and [FeTPPbipy](•) neutral radicals. These radicals are proposed to be formed by the reduction of metalloporphyrin, and the quantum-mechanical calculations are consistent with the fact that the acquired electrons are located on the phenyl groups of TPP.