The behavior of tungsten and molybdenum in extraction systems with binary extractants is investigated. The role of obtaining tungsten anhydride by purifying waste water from the redistribution is noted. The significance of binary extractants for the extraction of tungsten and molybdenum is underlined. Charts are presented to illustrate the quantitative dependence of the extracted substances. Salts of 4-tert.butylphenolate-, n.-caprylate-, di(2-ethylhexyl) phosphate- and di(2-ethylhexyl) were dithiophosphate trialkylbenzylammonium were used as extractants. Binary extractants have been found to provide efficient extraction and reextraction of tungsten and molybdenum. The maximum extraction of metals is observed at pH = 1–4. At pH> 8, the metals are present in the aqueous phase as mononuclear anions MoO42- and WO42-, and binary extractants are formed in the organic phase. Compared to amines and their salts, the solubility of the binary extractant in aqueous effluent redistribution decreases.