Four N-confused free-base tetraarylporphyrins containing an amino group on the inner carbon of the inverted pyrrole were synthesized and characterized as to their electrochemical and spectroelectrochemical properties in dichloromethane and N,N-dimethylformamide containing 0.1 M tetra-[Formula: see text]-butylammonium perchlorate as supporting electrolyte. The examined compounds are represented as (NH[Formula: see text](Ar)[Formula: see text]NcpH[Formula: see text], where “Ncp” is the N-confused porphyrin macrocycle and Ar is a [Formula: see text]-CH[Formula: see text]OPh, [Formula: see text]-CH[Formula: see text]Ph, Ph or [Formula: see text]-ClPh substituent on each meso-position of the macrocycle. Each porphyrin undergoes multiple irreversible reductions and oxidations. The first one-electron addition and first one-electron abstraction are located on the porphyrin [Formula: see text]-ring system to give [Formula: see text]-anion and [Formula: see text]-cation radicals with a HOMO–LUMO gap ranging from 1.21 to 1.34 V in CH[Formula: see text]Cl[Formula: see text] and 1.06 to 1.12 V in DMF. Both electrogenerated products are unstable and undergo a rapid chemical reaction to give new electroactive species which can be further reduced at more negative potentials or further oxidized at more positive potentials. The effects of the inner amino-substituent on the UV-vis spectra and electrochemical properties of the porphyrin are discussed, and comparisons made to data in the literature for both structurally related N-confused porphyrins containing an inner carbon NO[Formula: see text] group and derivatives without the inner substituent.