The electrochemical reduction of 2,3 prime -dinitrobenzidine (I) has been investigated in N,N-dimethylformamide solutions. Three diffusion-controlled polarographic waves were obtained. The first wave is due to a reversible single electron-transfer while the second and third waves result from irreversible processes involving one and two electron-transfers, respectively. The radical anion formed in the first step of reduction was confirmed by ESR technique. The red color compound formed due to 'ion association' after the second electron-transfer step gives rise to a polarographic 'minimum' and a 'dip' in the chronopotentiogram in addition to the new 'peak clusters' seen in cyclic voltammograms.