The electrocatalytic activity of bismuth considered as a low-cost and green electrode material was studied in reductive dechlorination processes. Cyclic voltammetry analyses showed that the Bi electrode exhibited a high catalytic activity to reduce alachlor, a chlorinated herbicide, in the aqueous medium at different pH values. Bulk electrolyses were performed at different potentials and pH values. Alachlor was reduced in deschloroalachlor, its dechlorinated derivative, with a high selectivity (96%) and a current efficiency of 48%. The reductive dechlorination of other chlorinated compounds with an activated carbon atom was then studied, showing that the bismuth electrode catalyzed the electroreduction of chloroacetamides, α-halocarbonyl, and α-haloallyl pollutants. Cyclic voltammetry experiments allowed us to propose a mechanism explaining the high catalytic activity of bismuth to reduce these families of compounds.