Abstract: The electrochemical synthesis silicon wires by electrorefining metallurgical grade silicon in thermally dried and pre-electrolyzed molten KF-NaF eutectic were studied at temperatures 800-900 oC using cyclic voltammetry and ac impedance. One oxidation peak at -0.14 V could be attributed to the reaction of Si to Si⁴⁺. A cathodic peak occurred at -0.56 V in the cyclic voltammogram and one response semicircle in the ac impedance spectrum was observed, supporting a one-step electrochemical reduction process of Si⁴⁺→Si. The electrochemical reaction of silicon was controlled by the diffusion process. The purity of electrorefined silicon wires was up to 99.999% by ICP-MS analysis.