Al-Si alloy could be prepared by carbon thermal reduction of fly ash, resulting in high value-added utilization of fly ash and environmental friendliness. This type of alloy with a low content of Al requires to be further refined in order to achieve its commercial use. Therefore, in this paper, Al-Si30 alloy （i.e., one type of Al-Si alloy produced by reduction of fly ash）is employed as the anode to produce pure Al and Si, respectively, by molten salts electrolysis. In the electrochemical cell, W is used as the cathode, and LiCl-KCl system is chosen as the electrolyte. Potentiostatic electrolysis is carried out at temperatures ranging from 400 to 600 ℃. Al is dissolved into the melt as Al3+, then reduced as pure Al at the cathode. At the same time, pure Si is left in the anode. The produced Al and Si are characterized by XRD, SEM and ICP analysis.