Abstract: The cathodic behavior of molten CaCl₂, CaCl₂-CaO and equimolar CaCl₂-NaCl-CaO was studied by cyclic voltammograms and constant potential polarization at temperatures of 1123 to 1173 K on molybdenum and titanium electrodes. The diffusion coefficient of Ca²⁺ (CaO) in molten CaCl₂-CaO was calculated from the linear relationship between the square root of scan rate and the peak current density. The deposition potentials and the potential temperature coefficient of CaO in molten CaCl₂-0.5mol%CaO and CaCl₂-NaCl-0.5mol%CaO were also obtained from their cyclic voltammograms. The result shows that CaO is more easily reduced than CaCl₂. The addition of NaCl in molten CaCl₂-CaO induces the underpotential electrodeposition of CaO.