The synthesis, optical spectroscopy, photophysical properties, electrochemistry, and X-ray photoelectron spectroscopy of a series of [5,10,15,20-tetrakis(perfluoroalkyl)porphinato]zinc(II) complexes and their free base analogs are reported. The title compounds were prepared by a condensation methodology that utilizes perfluoro-1-(2’-pyrrolyl)-1-alkanol precursors and employs continuous water removal throughout the course of the reaction to yield the meso perfluorocarbon-substituted porphyrins. The nature of the porphyrin-pendant meso-perfluoroalkyl group exerts considerable influence over the macrocycle’s solubility properties. The structure of the monopyridyl adduct of [5, 10, 15,20-tetrakis(heptafluoropropyl)porphinato zinc(II) features an S-4-distorted porphyrin core; X-ray data are as follows : with a = 15.1330(5) Angstrom, b = 19.2780(6) Angstrom, c = 14.6030(4) Angstrom, alpha = 110.220(2)degrees, beta = 103.920(2)degrees, gamma = 85.666(2)degrees, V = 3880.1(2) Angstrom(3), d(calc) = 1.887 g cm(-3), and Z = 4. Electrochemical studies carried out on these porphyrin and (porphinato)zinc(II) complexes indicate that meso-perfluoroalkylporphyrins are among the most electron-deficient porphyrinic species known. X-ray photoelectron spectroscopy experiments corroborate the electron poor nature of these systems and evince extreme stabilization of the nitrogen Is orbitals, consonant with particularly effective removal of electron density from the macrocycle by the meso-perfluoroalkyl moieties that is modulated by sigma-symmetry orbitals. The photophysical properties of these compounds differ from all other previously reported highly electron deficient porphyrin macrocycles in that they possess long-lived, fluorescent excited states; hence their optoelectronic features are consistent with a variety of excited-state electron-transfer quenching schemes in which both (ZnP)-Zn-1* and (H2P)-H-1* can be utilized as potent photooxidants.