The electro-reduction of chromium oxide（Cr2O3） was investigated in an equimolar mixture of CaCl2-NaCl molten salt at 800℃ for developing a more efficient process for chromium preparation. Cyclic voltammetry and potentiostatic electrolysis were used to study the electro-reduction of the Cr2O3-loaded metallic cavity electrode. In addition, a number of parameters affecting the rate and extent of Cr2O3 electrolysis were considered to better understand the electrolysis process. The results demonstrate that CaCl2-NaCl molten salt is applicable for preparing Cr directly from Cr2O3 and the electrolysis parameters exert great influence on the cathode product. Under optimal experimental conditions, nodular Cr with an oxygen content of 0.5%（mass fraction） was obtained without any chromium carbides detected by XRD. Furthermore, the relatively high solubility of CaO and quite rapid crystal growth result in the formation of large platelet CaCr2O4, and the addition of NaCl to CaCl2 results in several variations on the electrolysis process and the product morphology from pure CaCl2 molten salt.
