The cation exchange behavior of bismuth was studied on Dowex 50W-X8 with hydrochloric, sulfuric, nitric, and perchloric acids, with ammonium chloride and sodium nitrate as the eluting agents. The efficiency of eluants was evolved in terms of elution constant and volume distribution coefficient. Bismuth was separated from copper, cadmium, tin, aluminum, nickel, manganese, vanadium, magnesium, mercury, iron, zinc, silver, cobalty barium, and calcium by the gradient elution process. It was separated from lead, uranium, antimony, and strontium by selective elution with specific eluants. The oxyanions were separated from it by the selective sorption process. The method was found to be applicable to analysis of bismuth-based alloys.