Extraction of zinc(II) and iron(III) from hydrochloric acid solutions using quaternary phosphonium salts, Cyphos® IL 101, Cyphos® IL 104, Cyphos® IL109 and Cyphos® IL 111 in mixtures with toluene, was studied. Trihexyl(tetradecyl)phosphonium chloride (Cyphos® IL 101) and trihexyl(tetradecyl)phosphonium bis(2,4,4-trimethylpentyl)phosphinate (Cyphos® IL 104) showed the best zinc(II) and iron(III) extraction abilities. After three stages of zinc(II) extraction with Cyphos® IL 101 and Cyphos® IL 104 the efficiencies were 100 and 93.6%, respectively. Total iron(III) transport to the organic phase was achieved after two separation stages and amounted to 82.1 and 100% for Cyphos® IL 101 and Cyphos® IL 104, respectively. Zinc(II) and iron(III) could be effectively stripped from the loaded organic phases with 0.5 mol dm-3 sulfuric acid. The more hydrophobic the character of the anion type of phosphonium salts, the lower the efficiency of extraction.