The use of chemically modified chloromethylated polystyrene-PAN, CMPS-PAN (ion-exchanger) for the preconcentration and separation of total mercury after digestion in preparation for determination by cold vapour atomic absorption spectrometry (CVAAS) was described. The effects on the percentage of recovered mercury by mass change of ion-exchanger, stirring time, pH of the solution samples and eluent concentration were studied. The distribution coefficient K_d is 10^6.6 ml g⁻¹. The interfering effects of some foreign ions were described. The metal complex formed between CMPS-PAN ion-exchanger and mercury was characterized by IR spectroscopy, pH-metric titration and thermal analysis. The method is simple and rapidly applicable for the determination of total mercury (ng ml⁻¹) in natural water, milk and urine.