Abstract The behavior of milligram amounts of silver, bismuth, cadmium, and zinc in liquid-liquid extraction has been studied with 20% trioctylamine (TOA) in carbon tetrachloride. The results have also been applied to the separation of the four metals as their TOA complexes by extraction chromatography. After passing a sample solution of 2 M HCl through a column (φ1cm×1 30 cm) consisting of a stationary phase of TOA–CCl4 on Kel-F, the metal ions were retained and then eluted with 5.5 M HCl at the rate of 0.5–1 ml/min at 20±1 °C. Silver was found in 90–180 ml of the effluent; Bi was flowed down in 200–500 ml of the same effluent. The cadmium and Zn were held so firmly on the column that they could not be removed under the above conditions. Therefore, water was passed through to release these metals. Zinc was first flowed down with 0–50 ml, and then Cd, with 200–500 ml of water. When 5M HNO3 was used as the eluting solution instead of water, the Cd was immediately removed from the column. The percentage recovery of these metals in the extraction chromatography was estimated as 101% (Ag), 99% (Bi), 97% (Cd), and 94% (Zn) respectively. The distribution ratios of these metals, as obtained by the extraction chromatography of the TOA–carbon tetrachloride (Kel-F)–HCl system, were in quite good agreement with those obtained by the batch extraction.