The role of cobalt and iron corroles in catalytic CO2 reduction has been studied. Chemical, electrochemical, and photochemical reductions of the stable metal corroles Ph3PCoIII(tpfc) (tpfc = 5,10,15-tris(pentafluorophenyl)corrole), ClFeIV(tpfc), and ClFeIV(tdcc) (tdcc = 5,10,15-tris(2,6-dichlorophenyl)corrole) have been carried out in acetonitrile solutions. Stepwise reduction to the [MII(tpfc)]- and [MI(tpfc)]2- states was observed in all cases. Gradual reduction with sodium amalgam permitted recording of the optical absorption spectra of the various oxidation states and showed that the MI state reacts with CO2. Cyclic voltammetry in Ar-saturated acetonitrile solutions permitted determination of the following half-wave potentials: for Ph3PCoIII(tpfc), 1.11 V, 0.72 V, −0.42 V (Epc), −1.44 V, −2.3 V (Epc); for ClFeIV(tpfc), 0.44 V, −1.01 V (Epc), −1.60 V, −2.2 V (Epc); for ClFeIV(tdcc), 0.24 V, −1.18 V (Epc), −1.78 V vs SCE with a scan rate of 0.1 V s-1. Cyclic voltammetry in CO2-saturated solutions indic...