The electrochemical behaviour of various nitro substituted benzidine (NB) in amphiprotic (methanol-water mixtures) and dipolar aprotic (N, N-dimethylformamide, DMF) media yields interesting data. The reduction of these compounds at a mercury cathode in DMF containing 0. 1M tetrabutylammonium iodide (TBAI) supporting electrolyte shows two or more polarographic diffusion-controlled steps. The aim of this paper is to correlate the Huckel molecular orbital (HMO) data obtained for various nitro substituted benzidines with the experimental half-wave potential (E// one-half ) values obtained from polarography.