The electrochemical reductive cleavage of carbon-chlorine bond in 1-chloro-2,4-dinitrobenzene at gold electrodes is analyzed from a mechanistic point of view. The initial electron transfer forms the radical anion of 1-chloro-2,4-dinitrobenzene which subsequently undergoes bond cleavage following an EC mechanism. At low scan rates, the reduction is under the kinetic control by the chemical step, while the voltammetric wave becomes reversible at high scan rates and a mixed chemical-diffusion control is observed at intermediate scan rates. The cleavage rate constant of the carbon-chlorine bond has been deduced using the voltammetric data in conjunction with convolution analysis and the results have been verified by simulating the experimental voltammogram under the frame work of EC mechanism. © 2005 Elsevier Ltd. All rights reserved.