We develop a novel method of synthesizing 2,2'-dichlorohydrazobenzene (DHB) from o-chlornitrobenzene (o-CNB) in a membrane-separated cell on a porous Ni/Fe-combined electrode. PbO particles are used as a catalyst and are dispersed finely over and in the electrode surface. The morphology and microstructure characteristics of electrode materials are characterized by SEM and XRD analyses. The influences of the cathodic surface morphology, electrolyte temperature, and initial concentration of o-CNB are investigated by liquid chromatography and electrochemistry. A moderate current density (e.g., 5.2 A/dm(2)) and temperature (70 degrees C) are beneficial to improving hydrogenation reduction, current efficiency, and yield, which could reach 85% when density is adjusted and 91% when the temperature is adjusted. (C) 2010 Elsevier Ltd. All rights reserved.