Photoreduction of Fe(OEP) (OEP: octaethylporphyrin) in organic solvents by visible light was demonstrated to be a ligand-aided process in which simultaneous coordinations of a base such as 2-methylimidazole (2MeIm) and of an aliphatic alcohol to two axial positions of the iron ion were required. Coordination of an alcohol was evidenced from the observation of the Fe-alcohol stretching (nu-Fe-alcohol) resonance Raman (RR) band. Since this band exhibited an appreciable frequency shift between ROH and ROD, coordination of the alcohol in a protonated form was suggested. When a primary or secondary alcohol was added to the CH2Cl2 solution of Fe(III) (OEP)Cl in the presence of 2MeIm, a new absorption band appeared around 560-590 nm and the nu-Fe-alcohol RR band was most intense for excitation at the maximum of the new absorption band. The new absorption was therefore assigned to the alcohol to Fe(III) charge transfer (CT) band. A tertiary alcohol gave neither the CT band nor the nu-Fe-alcohol RR band, although some spectral changes were noticed after long laser illumination at 441.6 nm, and the photoreduction as seen for other alcohol solutions did not take place. This photoreduction was not apparently recognized in the presence of oxygen. However, flash photolysis experiments demonstrated that the photoreduction occurs irrespective of the presence or absence of oxygen but rapid reoxidation results in apparent no effect.