The extraction of lanthanides in spent fuel reprocessing plays a key role in the development of nuclear energy. In this work, the extraction of the typical fissionable cerium elements has been studied by electrolytic co-reduction of Al(III) and Ce(III) in LiCl-KCl-CeCl3 molten salts assisted by KAlCl4. The electrochemical behavior of the reduction of Al(Ⅲ) and Ce(Ⅲ) on a molybdenum electrode was studied by cyclic voltammetry (CV), square wave voltammetry (SWV), and open circuit chronopotentiometry (OCP), and specific peaks of five Al-Ce intermetallic compounds were detected. After 2.7 h of galvanostatic electrolysis at a current density of 0.064 A cm−2, the extraction efficiency and current efficiency of Ce(Ⅲ) reached 99.9 % and 91.3 % respectively. Potentiostatic electrolysis is slightly more efficient, with 99.9 % Ce(Ⅲ) extraction in 3.5 h at a current efficiency of 97.8 %. The products of electrolysis are rod-shaped alloys (Al11Ce3, Al3Ce, Al2Ce), and the molten salts purified by electrolytic separation are free of impurity signals and can be reused for electrolytic refining.