The subject of the paper is niobium extraction by solid extractants (TVEX) on the basis of tri-butylphosphate from hydrochloric and sulfuric media. Comparison with niobium solvent extraction was carried out. Mechanism of Nb removal by tri-butylphosphate (TBP) Liquid and introduced to TVEX matrix was established by means of Nb-93 and P-31 NMR spectroscopy. The data received allow to assume that niobium is extracted from 7 and 9 mol/l solutions niobium by both TBP and TVEX-TBP as [H3O .(m - 1)H2O . nTBP](+)[NbOCl4](-) anion complex, in which the metal is not bonded with TBP directly. At that time TVEX-TBP extracts Nb from 11 mol/l solution forming the complex [NbOCl4. TBP](-) in organic phase.