The anodic dissolution of niobium in carbamide + chloride melts has been studied by cyclic voltammetry and UV/VIS, ESR and IR spectroscopies, and the structure of the complex ions formed has been established. Over a wide current density range Nb transfers into the melt in the form of 5-valent ions only, coordinated with Cl ligands in octahedral [NbCl6](-). The possibility of cathodic reduction of these complexes to quasi-octahedrally coordinated [NbCl6](2-) was shown; spectral characteristics of both complexes are presented.