The interaction of molybdenum and tungsten of 2-hydroxy-5-halogentiophenol leading to the formation of extractable with chloroform ternary complex has been investigated. As hydrophobic amins aniline, N-methylaniline and N, N-dimethylaniline were used. Conditions for the extraction-photometric determination of molybdenum and tungsten have been found. It was found that the ternary complexes are formed at  pH_opt. 1.8–5.1. The maximum in the absorption spectrum is observed at 457–538 nm. The molar absorbance coefficient is in the range of (3.4–4.2)·10⁴. This fact can be regarded as an indication that Me(VI) is reduced to Me(V) by the reagent itself during the complex formation.