7-Ketolithocholic acid was synthesized by indirect electrooxidation of chenodeoxycholic acid using the medium of Br-/Br-2. Some important factors such as anode material, solvent, initial concentration of chenodeoxycholic acid, current density, electrolysis time have been investigated in detail. By comparing the experiment results, it can be concluded that productivity and current efficiency in the divided electrolytic cell are higher than that in the undivided electrolytic cell. The optimized process conditions have been found to be: the anode material PbO2/Ti, the solvent acetonitrile, and initial concentration of chenodeoxycholic acid 23.8-31.8 mg/mL, current density 95.2-142.9 A/m(2). The current efficiency could reach 85% and the productivity of 7-ketolithocholic acid could reach 83%. The melting point, IR spectrum, H-1 NMR, C-13 NMR and EI-MS were used to characterize the product. The analytical results confirm that the product is 7-ketolithocholic acid.