In this work the distribution coefficients (D) of polonium between 0.1 mol dm−3 TOPO/toluene; TOPO/cyclohexane; TBP/toluene and TBP/cyclohexane and aqueous solutions of inorganic acids (HCl, HNO3, H2SO4 and H3PO4) were determinated. The molarities of inorganic acids were between 0.5 and 12.0 mol dm−3. The activity of extracted Po-209 was measured by means of liquid scintillation counting. The best result was obtained for TOPO/toluene and 2 mol dm−3 H2SO4 system (D = 62 ± 9). The most stable conditions of extraction were found for TOPO/toluene-HCl system.