Influence of fluoro metallates acids H₂TiOF₄, H₂SiF₆ for the purpose of comparison H₂SO₄ on extraction Mo and W by tributyl phosphate is studied. It is shown that extraction of Mo and W increases among acids H₂SO₄ < H₂SiF₆ < H₂TiOF₄. Zone of anomalously high extraction of Mo and W (to 90 and 50% accordingly) with well-sounded maximum on the curves characterizing dependence of distribution Mo and W from concentration Ti is found for fluoride-titanous system at concentrating Ti of 1,0–1,5 mol/l. The obtained data is interesting for extraction technologies Ta and Nb in connection with the observable tendency of increase in volumes of processing of poor niobiumtantalic raw materials with the high impurity containing.