P-ferrocene-SA/acetylferrocene-CS Bipolar Membrane (BPM) was prepared with phosphorylated agent as the cation exchange layer, and chitosan (CS) modified with acetylferrocene as the anion exchange layer. Zinc/Nickel alloy layer was placed on the surface of cation exchange layer to realize zero polar distance in the cathode chamber. The 2, 3, 5, 6-tetrachlopyridine (2,3,5,6-TCP) was electro-synthesized by reducing of pentachloropyridine(PCP). At the current density of 30mA·cm-2, the current efficiency was 70.1% and the yield of 2, 3, 5, 6-TCP was up to 96%. Compared with the traditional method, the electro-generation technology greatly eliminated the environmental pollution.