In a previous study, the authors showed that iron(III) [ tetrakis(pentafluorophenyl)] porphyrin chloride [(F20TPP)FeCl]is catalytically inactive for cyclooctene epoxidation by hydrogen peroxide in acetonitrile but is catalytically active if the solvent contains methanol. It was suggested that the precursor to the active species is (F20TPP)Fe(OCH3) in methanol-containing solvents. The present study was aimed at evaluating this hypothesis. (F20TPP) Fe(OCH3) was synthesized and characterized by H-1 NMR but was found to be inactive in both acetonitrile and methanol. Further investigation of the interactions of (F20TPP) FeCl with methanol in acetonitrile/methanol mixtures was then carried out using NMR. Two species, characterized by H-1 NMR resonances at 82 and 65 ppm, were observed. The first resonance is attributed to the, ss-pyrrole protons on molecularly dissolved (F20TPP) FeCl, whereas the second is attributed to,-pyrrole protons of [(F20TPP) Fe](+) cations that are stabilized by coordination with a molecule of methanol, viz., [(F20TPP) Fe(CH3OH)] +. The relative concentration of [(F20TPP) Fe(CH3OH)](+) increases as the fraction of methanol in the solvent increases, suggesting that methanol facilitates the dissociation of (F20TPP) FeCl into cations and anions. A thermodynamic model of the dissociation is proposed and found to describe successfully the experimental observation over a range of solvent compositions, porphyrin concentrations, and temperatures. UV-visible spectroscopy was also used to validate the developed model. In addition, the observed rate constant for cyclooctene epoxidation was found to be proportional to the concentration of [(F20TPP) Fe(CH3OH)](+) calculated using the thermodynamic model, suggesting that this intermediate is a precursor to the species that catalyzes olefin epoxidation. The catalytic activity of [(F20TPP) Fe(CH3OH)](+) was further confirmed through experiments in which (F20TPP) Fe(OCH3) dissolved in methanol was reacted with HCl(aq). This reaction produced a product with an NMR peak at 65 ppm attributable to [(F20TPP) Fe(CH3OH)](+), and this mixture was found to have activity for cyclooctene epoxidation similar to that of (F20TPP) FeCl dissolved in methanol.