Eleven free-base corroles with different electron-donating or electron-withdrawing meso substituents were characterized as to their electrochemistry and UV-visible spectroscopy in benzonitrile (PhCN) or pyridine containing tetra-n-butylammonium perchlorate (0.1 M). Six forms of the compounds with different numbers of protons and/or oxidation states were spectroscopically identified and are represented as (Cor)H-3, ((center dot)Cor)H-2, [(Cor)H-2](-), [((center dot)Cor)H-2](2-), [(Cor)H-4](+), and [((center dot)Cor)H-4](2+), where Cor is a trianionic corrole macrocycle. The electrochemistry and UV-visible properties are a function of corrole basicity, solvent basicity, and types or sizes of the meso substituents, and the compounds could be subdivided into one of two different groups, one of which comprises sterically hindered corroles and another that does not. The electroactive species in PhCN is (Cor)H-3, whereas in pyridine, one inner proton dissociates, generating a mixture of (Cor)H-3, [(Cor)H-2](2-), and pyH(+). The addition of one electron to [(Cor)H-2](-) reversibly gives the [((center dot)Cor)H-2](2-) pi-anion radical, whereas a reversible oxidation of the same species gives the neutral radical ((center dot)Cor)H-2. The first one-electron reduction of (Cor)H-3 occurs at the macrocycle in PhCN, but the initial product rapidly converts to [(Cor)H-2](-), which undergoes additional reversible redox reactions at the conjugated pi-ring system. The first oxidation of (Cor)H-3 in PhCN leads to a mixture of ((center dot)Cor)H-2 and [(Cor)H-4](+), both of which could be further oxidized or reduced. The UV-visible spectra of [(Cor)H-4](+) were measured in PhCN after titrations with trifluoroacetic acid, after which selected samples were examined as to their electrochemistry. The HOMO-LUMO gaps of [(Cor)H-2](-), (Cor)H-3, and [(Cor)H-4](+) were also determined.