In the present paper, an on-line preconcentration procedure for determination of cadmium, copper and zinc by thermospray flame furnace atomic absorption spectrometry (TS-FF-AAS) is proposed. Amberlite XAD-4 functionalized with 3,4-dihydroxybenzoic acid (XAD4-DHB) packed in a minicolumn was used as sorbent material. The metals were retained on the XAD-DHB resin, from which it could be eluted directly to the thermospray flame furnace system. The detection limits were 28 (Cd), 100 (Cu) and 77ngL −1 (Zn) for 60s preconcentration time, at a sample flow rate of 7.0mLmin −1 . Enrichment factors were 102, 91 and 62, for cadmium, copper and zinc, respectively. The procedure has been applied successfully to metal determination in biological standard reference materials.