The electrochemical behaviors of a series of four intramolecular hypervalent complexes containing Sb...N bonding (antimony (III, V) compounds) and of the relevant common precursors, organonitrogen and (tri- and penta-) substituted stibines, have been investigated using cyclic voltammetry. The shape of the voltammograms is not the simple superposition of the precursors, and the antimony centers of all the complexes undergo an irreversible oxidation process consisting of a charge transfer preceded by the first-order formation-dissociation equilibrium of the complexes. The detailed analysis of the oxidation current, when combined with the theoretical treatment by Nicholson and Shain, provides information on the status of the Sb...N bonding. Good correlations between the electrochemical parameters derived from the oxidation current and the Sb...N bond distance are obtained. Additionally, the cyclic voltammetry of a mixture of the precursors leads to the discovery of their intermolecular hypervalent complexes.