Studies were performed to investigate the cathodic behavior of silicon (IV) ion in a BaF2-CaF2-SiO2 melt at a temperature of 1573 K. The results obtained show that the silicon (IV) ion was reduced through a single-step from Si4+ + 4e = Si, which was an irreversible process with diffusion-controlled mass transfer. The diffusion coefficient (D) for the reduction process of silicon (IV) ion in BaF2-CaF2-SiO2 melt was 9.76 x 10(-5) cm(2) s(-1), at 1573 K. Furthermore, galvanostatic electrolysis performed on a molybdenum electrode, which further presents the feasibility of electro-depositing silicon in molten BaF2-CaF2-SiO2 system. (C) 2013 The Electrochemical Society. [DOI: 10.1149/2.038303jes] All rights reserved.