Cyclic voltammetry and controlled-potential (bulk) electrolysis have been used, along with gas chromatography (GC) and gas chromatography–mass spectrometry (GC–MS), to investigate the electrochemical reductions of 2-bromo-5-chlorothiophene (1), 3-bromo-2-chlorothiophene (2), and 2,5-dibromothiophene (3) at silver cathodes in dimethylformamide (DMF) containing 0.050M tetramethylammonium perchlorate (TMAP) as the supporting electrolyte. Cyclic voltammograms for each compound exhibit two irreversible cathodic peaks that correspond to successive cleavage of the relevant carbon–halogen bonds. Controlled-potential electrolyses of 2-bromo-5-chlorothiophene revealed a two-electron cleavage of the carbon–bromine bond to afford 2-chlorothiophene as the major product along with traces of 3-bromo-2-chlorothiophene and 4-bromo-2-chlorothiophene, each arising from occurrence of a halogen dance. Bulk electrolysis of 3-bromo-2-chlorothiophene produces only 2-chlorothiophene in a two-electron process. Controlled-potential electrolysis of 2,5-dibromothiophene yields only 2-bromothiophene, via a process that involves a carbanion intermediate. A mechanistic scheme for the two-electron reduction of 2-bromo-5-chlorothiophene (1) is proposed that accounts for the formation of 2-chlorothiophene as well as two minor products that arise via a halogen dance.