An ICP-OES method for applying a macroporous ploy(vinylethy-lenediamine) chelating resin to preconcentrate and separate trace Ga(III), In(III), Bi(III), Sn(IV) and Pb(II) ions from solution samples is established. The analyzed ions of 0.05–0.5 ug/ml can be enriched by the resin of 0.07-g amount at a 1.0 ml/min of flow rate at pH 5, and can be also desorbed with a 10 ml of 3 M HClO4from the resin column, with recoveries over 96%. The chelating resin reused 7 times can still adsorb quantitatively the Ga, In, Bi, Sn and Pb ions, and a 500-fold excess of Fe(III), Al(III), Mn(II), Cu(II), Ni(II), Zn(II) and Cr(III) caused little interference with the enrichment and determination of these ions. The RSDs of the proposed method are in the range 1.2–5.5% for each analyzed ion. The recoveries of added standard in real solution samples are between 94% and 100%, and the concentration of each ion in a mineral sample detected by the method is in good agreement with the analyzed value by ETAAS method.