The electrochemical behaviors of nitrobenzene at a pyrolytic graphite electrode modified with carbon nanotubes (CNTs) were studied using cyclic voltarnmetry and constant-potential electrolysis technique, and the CNT-modified electrode was characterized with Fourier transform infrared spectroscopy (FTIR), high resolution transmission electron microscopy (HRTEM) and scanning electron microscopy (SEM) measurements. A CNT-modified packed-bed flow reactor was also constructed for electrocatalytic reduction of nitrobenzene. The results showed that CNTs exhibited high activity for nitrobenzene reduction to aniline and the electrochemical reduction of nitrobenzene at CNT-modified electrode followed the pathway of nitrobenzene -> phenylhydroxylamine -> aniline. CNTs had been functionalized with profuse carboxylic group and other oxygen-containing groups, became open with some lacuna on the wall, and were distributed symmetrically on the electrode with forming a three-dimensional layer, resulting in the high catalytic-activity for nitrobenzene reduction to aniline. The removal of nitrobenzene was over 95% with electrolysis for 50 min at - 1.20 V in pH 5 solution using the CNT-modified packed-bed flow reactor, and no other product was obtained except aniline. The removal of nitrobenzene was over 95% with electrolysis for 80 min at - 1.20 V in pH 7 solution and was 87% with electrolysis for 120 min in pH 9 solution. A little phenylhydroxylamine besides aniline was obtained during the initial electrolysis stage, and then all reduced to aniline. The average current efficiency at pH 5, 7 and 9 was 46, 51 and 63%, respectively. The electrolysis. products were mineralized easily through aerobiotic biodegradation. (c) 2007 Elsevier B.V. All rights reserved.