In order to investigate the possibility of electroseparation of CaCl2 from CaCl2-LiCl-KCl melts prior to Li* reduction, Ca2+ and Li ions reduction potentials in the melts were investigated by cyclic voltammetry (CV) and chronopotentiometry (CP) on both a tungsten and a tin electrodes. The potential difference between the two ions in CaCl2 (0.5 wt%)-LiCl-KCl melts was 0.2V at 953 K analyzed by CV. About 0.4V reduction potential difference between Ca2+ and Li+ ions was observed on chronopotentiograms recorded on a tungsten electrode in CaCl2 (2.0 wt%)-LiCl-KCl melts either at 723 K or 953 K, which can meet the requirements of total electroseparation. Tin electrode can shift the reduction potentials of Ca2+ and Li+ to more positive ones and also can improve Ca deposition rate and removal efficiency. After 3.0 h electrolysis on solid tungsten at -3.4V vs. Cl-2/Cl- and liquid tin cathode at -3.0 V vs. Cl-2/Cl-, the Ca/Li (weight ratio) in the melts changed from 3/25 before electrolysis to 2.6/25 and 0.76/25 respectively, analyzed by ICP. Under stirring, even higher removal rates of 83.65 wt% and 94.66 wt%, corresponding to 0.54/25 and 0.16/25 of Ca/Li have been obtained for 3.0 h and 6.0 h electrolysis at -3.0 V vs. Cl-2/Cl- on a tin electrode. Clearly, stirring availably increases the Ca2+ ions diffusion rate and its electrochemical reaction rate. (C) 2011 Elsevier Ltd. All rights reserved.