Cyclic voltammetry and controlled-potential (bulk) electrolysis have been employed to investigate the reduction of 4,4′-(2,2,2-trichloroethane-1,1-diyl)bis(chlorobenzene) (DDT) at silver cathodes in dimethylformamide (DMF) containing 0.050M tetramethylammonium tetrafluoroborate (TMABF 4 ). In addition, this work has been extended to the individual reductions of two degradation products, namely 4,4′-(2,2-dichloroethane-1,1-diyl)bis(chlorobenzene) (DDD) and 4,4′-(ethene-1,1-diyl)bis(chlorobenzene) (DDNU). At a scan rate of 100mV s −1 , cyclic voltammograms for irreversible reduction of DDT at a silver electrode exhibit four prominent cathodic peaks in DMF and CH 3 CN, and three prominent cathodic peaks in DMSO. On the other hand, reduction of DDD and DDNU at silver in DMF–0.050M TMABF 4 displays four and two irreversible peaks, respectively. Carbon–chlorine bonds of the –CCl 3 moiety of DDT and of the –CHCl 2 moiety of DDD are reduced more easily at silver than at glassy carbon. Bulk electrolyses of DDT at a silver gauze cathode in DMF–0.050M TMABF 4 afford a potential-dependent mixture of products that includes DDD, DDNU, 4,4′-(2,2-dichloroethene-1,1-diyl)bis(chlorobenzene) (DDE), 4,4′-(2-chloroethene-1,1-diyl)bis(chlorobenzene) (DDMU), 4,4′-(2-chloroethane-1,1-diyl)bis(chlorobenzene) (DDMS), 1-chloro-4-(1-phenylvinyl)benzene (PVB), 1,1′-diphenylethylene (DPE), and 1,1′-ethylidenebisbenzene (EBB). However, at more negative potentials, the principal products are completely dechlorinated DPE and EBB. Dechlorination of DDT at silver appears to proceed via a series of steps involving carbanion intermediates arising from direct reduction of alkyl and aryl carbon–chlorine bonds along with hydroxide-promoted E2 elimination of chloride. When DMF-d 7 was used as solvent, no evidence for deuterium atom incorporation into any product was seen, which indicates that radical intermediates do not play a significant role in the reduction of DDT.