To date, there are a number of methods for selective extraction of transition metal ions based on liquid-liquid extraction. One of the most interesting methods of metal ions extraction is liquid-liquid extraction with application of ionic liquids based on quaternary ammonium bases and organic acid residues, in particular, organophosphorus, diluted with organic solvent (toluene, xylene, kerosene, etc.). However, using of organic solvents does not correspond to the modern tendencies of harmful effects on the environment reducing. Thus, we propose to use Aliquat 336 and D2EHPA-based ionic liquid for extraction of transition metal ions in ecologically safe aqueous two-phase system based on polypropylene glycol 425 and sodium chloride. Di(2-ethylhexyl) phosphate trioctylmethylammonium has been shown to yield more than 80% Fe(III) and Y(III) ions.