The reduction mechanism of nitrobenzyl bromide isomers has been revisited using spectro-electrochemical techniques so as to address a number of unsolved questions concerning the electrochemical behavior of nitrobenzyl bromides in aprotic solvents. The reaction intermediates have been spectroscopically characterized in terms of their transient absorption spectrum, and their life time and reduction potential have been determined. The nature of the reduction products yielded after the electrolysis process is a function of the applied potential, which is strongly related with the evolution of the radical. (C) 2009 Elsevier Ltd. All rights reserved.