The reaction of meso-triarylcorroles with AgNO2 proceeds with concomitant metalation and peripheral substitution to give the corresponding nitro-substituted silver(III) corrole complex. The substitution is highly regioselective, giving only the corresponding 3-nitro derivative, among the different possible isomers. The results obtained indicate that the reaction intermediate-is the pi-cation radical of the complex, which is then attacked by nitrite ion. This was proven by the reaction of the copper corrole complexes with NaNO2: in this case, the nitration reaction proceeded without the addition of an oxidant, because of the pi-cation radical character of the copper complex. The reaction is also successful in the case of 2,3,17,18-tetraethyl-8,12-diacetoxymethyl-7,13-dimethylcorrole (AMCorH(3)), with the formation of the meso-substituted silver corrole derivative (NO2)(3)AMCorAg (fully characterized by X-ray crystallography), the first of its kind to be reported. Two of the corroles are characterized by,cyclic voltammetry and spectroelectrochemistry in dichloromethane, and the site of electron transfer is elucidated.