Résumé : The electrochemical behavior of several calcium antagonists of the dihydropyridine family has been investigated in aqueous buffered solution using a glassy carbon electrode. Both oxidation of the dihydropyridine ring and the reduction of the nitro or benzoxadiazole moiety are observed using cyclic voltammetry and the shape of the voltammograms depending on the initial scan direction. Each process may interfere with the other. The single reduction peak corresponds to a four‐electron transfer giving rise to the hydroxylamine. Reversing the scan leads to the nitroso derivative, its reversibility depends on the 2‐ or 3‐position of the nitro group. Oxidation of the dihydropyridine ring proceeds through a two‐electron exchange. However, nicardipine, which possesses a dialkylbenzylamine side chain, exhibits two additional peaks; the first due to the methoxylation of the side chain, and the second attributed to the oxidative chlorination of this moiety. Potentials are pH dependent. A general EC mechanism is proposed for the overall process. Copyright © 1992 VCH Publishers Inc.