A selective method has been developed for extraction chromatographic studies of Cu II and Bi III with Aliquat-336 (liquid anion exchanger) coated on silica gel as a stationary phase. Quantitative extraction of Cu II has been achieved at 4.0-6.0 M HCl and quantitative extraction of Bi III has been achieved at 0.1-4.0 M HCl, 0.1-6.0 M HNO 3 and 1.0-3.0 M H 2 SO 4 . The effects of different acids, stripping agents, flow rate on extraction and elution have been investigated. Cu II and Bi III have been separated from several metal ions. In order to assess the possible analytical application, both the metal ions have been separated from several multicomponent mixtures containing metal ions commonly associated with it. Attempts have been made to extract Cu II from standard alloy and ore samples. The proposed method is simple, rapid and selective.