Abstract: The electrochemical behavior of Li2CO3 in KCl-LiCl melt was investigated by continuous pulse-oscillograph and potential sweep. It was found that there is a peak of oxidation current ahead of the potential at which the negative chlorine ions precipitate and the current peak is caused by the CO2 which is produced by the O^2- ionic discharge due to Li2CO3 addition. In the KCl-LiCl system the back EMF increases with increasing current density, but the back EMF will decrease greatly at the same current density if adding Li2CO3. Using Li2CO3 instead of LiCl as the raws material in metallic lithium production by galvanolysis is regarded as the new trend of lithium galvanolysis because Li2CO3 will not only minimize the environmental pollution but also reduce the cost.