Electrochemical dechlorination of 2-chloro-5-trichloromethylpyridine (TCMP) to 2-chloro-5-chloromethylpyridine (CCMP) has important industrial application value in the preparation of imidacloprid. In this work, the influence of various process conditions (such as supporting electrolyte, cathode materials and their mesh number, temperature and current density) on the dechlorination, and the dechlorination potentials of TCMP and its dechlorinated products were investigated using bulk electrolysis experiments. The experimental results show that lithium acetate is the best choice among lithium acetate, lithium chloride, lithium perchlorate, ammonium chloride and tetrabutyl ammonium perchlorate. The yield of CCMP on each cathode material decreases in the following order: Cu > Pb > graphite > Ag > Zn > Ni. Under optimized process conditions (catholyte: methanol solution containing 10 φ(%) CH3COOH 5 φ(%) H2O 0.2 mol/L CH3COOLi 0.1 mol/L TCMP, cathode: 80 mesh copper, temperature: 30℃, the current density: 333 A/m2 at the early stage of reaction and 166 A/m2 at the last stage of reaction), 0.1 mol/L TCMP could be selectively dechlorinated to CCMP with the yield of 56.9%. The dechlorination po-tential of TCMP to DCMP is more positive than that of DCMP to CCMP, and the later is almost same to that of CCMP to CMP.