The interaction of iron(III) with 2-hydroxyhalogenthiophenolS in the presence of hydrophobic amine – anyline and N,N-dimetilanyline has been studied. From halogenthiophenols there were used 2-hidroxy-5-chlorothiophenol aND 2-hidroxy-5-bromothiophenol. The optimum conditions of complex formation and extraction have been found. The maximum extraction is reached at pH  3.8–6.2. The components ratio in the complexes Fe(III):HTPh:Аm=1:2:2. By Nazarenko’s method it was determined that the complex forming ion is Fe(OH)²⁺. The calculations made have indicated to that different ligand complexes in an organic phase don’t polymerize and exist in monomeric form (g=1.03–1.07). There has been estimated reaction selectivity. The complexes charge has been established by the tests on electromigration in U-shape tube and ion exchange on anionite EDP-10P.