The electrochemical reduction of carbon-halogen bonds in 5-bromo-1,3-dichloro-2-iodobenzene follows quadratic activation-driving force relationship except in one of the carbon-chlorine bonds. The variation of the transfer coefficient with the electrode potential has been estimated using the voltammetric data coupled with the convolution analysis. The standard potentials pertaining to the reduction of carbon-halogen bonds are evaluated using the Marcus theory of outer sphere electron transfer. © 2004 Elsevier Ltd. All rights reserved.