Abstract: In this paper, the electrochemical behavior of some elements, such as 210Po, Bi, Ag, Sb, Cu in HNO3-Bi-210Po and HCl-Bi-210Po systems with rather high bismuth content was investigated. The critical depositing potentials of these elements were determined under practical conditions and a chemical process for the separation and purification of 210Po from reactor irradiated bismuth oxide by controling cathode potential was described.The γ energy spectrum of 210Po obtained by this method was examined by multichannel analyzer with Ge (Li) detector and no γ impurity was found. The chemical purity of 210Po was also found to be very high. By the electrolysis in HNO3-Bi-210Po and HCI-Bi-210Po systems, up to 45 Ci/cm2 and 16.2 Ci/cm2 of 210Po deposited on Au (or Pt) foil have been obtained respectively. The thin layer of 210Po deposition is uniform and adheres strongly to the foil. Our results showed that, by the electrolysis in HNO3-Bi-210Po system, the quality of deposit of 210Po on Au (or Pt) foil was better than that in HCl-Bi-210Po system.The advantage of this chemical process developed is that 210Po can be separated from the irradiated Bi2O3 target, purified and made into a variety of 210Po sources with different intensity simultaneously.