Studies were conducted to investigate the cathodic behavior of Fe (III) ion in a CaO-MgO-Al2O3-SiO2-NaF-Fe2O3 melt at 1673 K. The kinetic parameters for the charge transfer steps and the reduction mechanism of Fe (III) were investigated by cyclic voltammetry and square wave voltammetry. The results show that two steps are involved during the electrochemical reduction of Fe (III): Fe3+ + e -> Fe2+, Fe2+ + 2e -> Fe. Meanwhile, galvanostatic electrolysis was performed on a molybdenum electrode, which further presents the feasibility of electro-depositing iron in the molten CaO-MgO-Al2O3-SiO2-NaF-Fe2O3 system. (C) 2016 The Electrochemical Society. All rights reserved.