This work was accomplished in the context of systematic examination of a role played by electrolyte cation composition in electroreduction processes. The electrochemical behaviour of molten salts systems where CsCl was used as solvent for potassium and caesium, oxyfluorotantalates was investigated. In particular, the influence of the electrolysis parameters, such as concentration of tantalum species in electrolyte, temperature and current density on the cathodic products phase composition was determined by X-ray diffraction and scanning electron microscopy. Several phases generally crystallized at the cathode simultaneously. Among identified phases were metallic tantalum in cubic (alpha) and tetragonal (beta) crystal modifications and TaO. But the most characteristic phases for the melt under study were two isostructural compounds with pyrochlor type crystal lattice CsTa2+z (O5+yF1-y)-O-5 and CsTa2+z5-xO5+yF1-y. The former deposited in the form of transparent dielectric crystals and the later-in the form of metal-like conductive ones. This latter compound seems to be synthesized for the first time. The peculiarities of its structure were described. Electrochemical redox processes in melts containing potassium oxyfluorotantalates dissolved in CsCl were studied by cyclic voltammetry. Three discharge peaks were detected on voltammograms in the temperature range 700-850 degrees C. They were associated with the discharge of TaOF63- and TaO2F43- complexes and alkali metal cations. (c) 2006 Published by Elsevier Ltd.