The effect of the hypophosphite ion on the electrochemical reduction of nitrobenzene on Ni was evaluated from a cyclic voltammetric study and from constant potential electrolysis in an aqueous-ethanol alkaline medium. The results were compared with the data obtained in an hypophosphite-free solution. It was found that in an hypophosphite containing solution an unusual selective reduction of nitrobenzene to nitrosobenzene occurs. It is the first time that nitrosobenzene is detected as the reaction product of the nitrobenzene electrochemical reduction in an aqueous-ethanol solution. It is proposed that the Ni modified surface which is formed upon hypophosphite oxidation is responsible for the non reducibility of nitrosobenzene. The effect of the electrode potential on the nitrobenzene electrolysis on a Ni modified electrode was analysed. It was concluded that the highest nitrosobenzene yield (33%) and selectivity (82%) is achieved at -1.1 V. It was also found that the formation of nitrosobenzene leads to an electrode poisoning effect in the electrolysis process. (C) 2003 Elsevier Science Ltd. All rights reserved.