A novel pyroprocess is proposed to recover actinides from spent nuclear fuels, in which a liquid Ga is used as the key electrode material to achieve a high actinide/lanthanide separation efficiency. To evaluate the proposed pyroprocess, it is necessary to clarify the separation performance in the system of LiCl-KCl/liquid Ga electrode. In this study, an electrochemical actinides recovery was conducted by galvanostatic electrolysis of the liquid Ga electrode in LiCl-KCl melts containing both actinides (U, Pu and Am) and lanthanides (Ce, Nd, La and Gd) chlorides at 773 K. The obtained Ga alloy after the electrolysis was analyzed quantitatively to calculate the separation factors of Pu and Am based on Ce. The calculated separation factors in LiCl-KCl/liquid Ga electrode system were more than 10 times higher than those in LiCl-KCl/liquid Cd system.