The behavior of zirconium and hafnium in PEG 2000-Na2SO4-HCl aqueous biphasic system has been investigated. The dependences of HCl concentration (0.185-0.55 M), extraction temperature (298-318 K), and extraction time (5-120 min) on distribution ratios have been determined. Extraction of this metals in PEG 2000-Na2SO4- H2SO4 and PEG 2000-Na(3)Cit-HCl systems has been also studied. The sulfate and citrate complexes of Zr and Hf prefer salt-rich phase in contrast to chloride complexes which pass into PEG rich phase in about 50% (w/w) to the greatest degree in room temperature and at short extraction time. The increase of distribution ratios (D-Zr(*) = 3.75, D-Hf(*) = 4.31) was observed after addition of water soluble organic ligand - tiron (4,5-dihydroxy-m benzenedisulfonic acid disodium salt). The results obtained in studied conditions are not very useful for the separation of zirconium and hafnium.