Distribution of iron (III), thallium (III, gallium, titanium (IV) chloride complexes in sodium chloride – synthanol DS-10 – water and ammonium sulfate – synthanol DS-10 – water systems, as well as iron (III), cobalt , nickel, cadmium and copper (II) thiocyanate complexes in the ammonium sulfate – synthanol DS-10 – water system investigated. It was found that the main influence on extraction is exerted by solution acidity and nature of the salting-out agent. The conditions for quantitative extraction of thallium (III) and gallium in the form of chloride complexes, as well as the conditions for maximum extraction of iron (III), zinc and cobalt thiocyanate complexes are established.