Electrochemical dechlorination of chlorobenzene in organic solutions was studied. Electrolysis of chlorobenzene in acetonitrile solution in a one-compartment cell fitted with a platinum cathode and a zinc anode at 60mA/cm(2) and 0 degrees C was found to be the optimum conditions, which gave complete dechlorination of chlorobenzene. However, similar result could not be achieved when applying these conditions to 1,3-dichlorobenzene and 1,2,4-trichlorobenzene. We found that the use of naphthalene which reacted as a mediator in the appropriate system could accelerate the reduction and gave complete dechlorination of those chlorobenzenes. Moreover, in the presence of naphthalene the reaction time could be shortened by half compared to dechlorination in the absence of naphthalene.