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Cyclic voltammetry and controlled-potential (bulk) electrolysis have been employed to investigate the direct electrochemical reduction of acetochlor (1) at carbon and silver cathodes in dimethylformamide. Voltammograms of1exhibit a single irreversible cathodic peak at both cathode materials. Catalytic properties of silver towards carbon–halogen bond cleavage are evidenced by a positive shift in the reduction of acetochlor as compared to the more inert glassy carbon electrode. Voltammograms in the presence of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), and comparisons of calculated relative interaction energies between acetochlor, possible intermediates, and deschloroacetochlor in the presence of different proton donors, suggest strong hydrogen-bonding interactions between HFIP and a carbanion intermediate. Addition of HFIP to electrolysis conditions promotes complete reduction at both cathode materials, with formation of deschloroacetochlor in high yields. In deuterium labelling studies, the use of DMF-d₇led to no evidence for deuterium atom incorporation. However, when HFIP-OD or D₂O were employed as a proton source, substantial amounts of deuterated deschloroacetochlor were observed. A mechanism for the reduction of acetochlor is proposed, in which radical intermediates do not play a significant role in reduction, rather a carbanion intermediate pathway is followed.