The electroreduction of polychloromethanes and polychloroethanes has been studied by means of cyclic voltammetry (CV) and preparative electrolysis experiments in acetonitrile (ACN), dimethylformamide (DMF) and their admixtures with water. Silver has been used as cathode material, on account of our extended experience on its well established electrocatalytic activity toward reductive dehalogenation reactions of organic compounds. Polychloro-methanes and -ethanes are common chlorinated solvents pertaining to the large family of volatile organic halides (VOH), whose high toxicity, or even carcinogenicity, demands careful treatment of contaminated soils, drinking waters and gaseous emissions. The results confirm the electrocatalytic role of silver and suggest a general route for the development of appropriate degradation processes.