In this work, a simple group separation scheme based on extraction for NAA determination of trace of As, Cd, Hg, Cu and Zn in biological materials is described. For this purpose, zinc-diethyldithiocarbamate, Zn(DDC)2, and methyl isobutyl ketone-iodide have been chosen as reagents. The elements can be extracted successively and quantitatively from strong mineral acids without adjusting pH of the solution, and separated into two groups suitable for gamma-ray spectrometry. Samples of 100–200 mg dry weight were double-sealed into polyethylene bags and irradiated in a swimming pool reactor with a thermal neutron flux of 1013n·cm–2·s–1 for 44 hours. After a cooling period of 1–3 days, the samples were digested with microgram quantities of carrier in concentrated nitric acid and sulfuric acid at 150°C for 3.5 hours in a teflon bomb, then extracted as described above. The reliability of the analytical method was checked using reference materials Horse Kidney IAEA H-8, Human Hair NIES-5 and Tomato Leaves NBS-1573. Most of the results obtained for reference materials agreed with the certified values12. Chinese autopsy samples of hair and liver were presented.