Electrolyte was prepared by introducing gaseous ReF6 into the molten LiF-NaF-KF eutectic at 600 degreesC. The electrochemical properties of the solutions were studied by voltammetric techniques. The reduction of ReF82- to Re occurred via a single irreversible step with diffusion controlled mass transfer. The diffusion coefficient of ReF82- was 8 x 10(-)10 m(2) s(-1) and the cathodic transfer coefficient was 0.13. Well-crystallized pure rhenium layers, up to 50 mum thick, were obtained on W, Ag, graphite and vitreous carbon substrates and were examined by SEM and X-ray diffraction techniques.