The electroreductive dechlorination of gamma-hexachlorocyclohexane (lindane) was investigated in non-aqueous media using as a catalyst the dirhodium complex Rh-2(dpf)(4), where dpf = the anion of N, N'-diphenylformamidinate. Rh-2(dpf)(4) undergoes two reversible one-electron redox processes in pyridine and/or N,N'-dimethylformamide (DMF), corresponding respectively to Rh-2(4+)/Rh-2(5+) and Rh-2(4+)/Rh-2(3+). Electrochemical and spectroelectrochemical measurements indicate that lindane reacts with the Rh-2(3+) center in singly reduced [Rh-2(dpf)(4)](-), giving a transient carbon-bonded dirhodium complex along with Cl-. Further catalytic de chlorination of lindane subsequently occurs with the activity of Rh-2(dpt)(4) as a catalyst depending upon the solvent conditions. Rh-2(dpf)(4) shows a higher catalytic reduction current in pyridine than in DMF for the degradation of lindane. This catalytic current can be further enhanced if 6% water (v/v) is added to the pyridine solution. Bulk controlled-potential electrolysis combined with GC-MS verified that although the addition of water to the neat pyridine increased the catalytic activity of Rh-2(dpf)(4), neat pyridine is still a better solvent for the formation of more extensively dechlorinated products of lindane. In neat pyridine, lindane can be converted stepwise to tetrachlorocyclohexene, dichlorobenzene isomers, chlorobenzene and the fully dechlorinated product benzene, the last of which becomes predominant at the end of the electrolysis. In pyridine having 6% added water, other than those dechlorinated products seen above, trichlorobenzene isomers are formed upon lindane degradation. Meanwhile, the relative concentrations of dichlorobenzene isomers and chlorobenzene become higher, while the yield of benzene becomes lower than the corresponding results obtained in neat pyridine. Based on the measured distribution of the products under the different solvent conditions, an overall pathway for the degradation of lindane is proposed.