A new Si refining process, which employs molten salt electrolysis and precipitation steps, is proposed and tested. In this process, impure Si is added to a Cu-Si liquid alloy anode, and the electrorefining of Si is conducted using an Al-Si liquid alloy cathode in a fluoride-based molten salt. From the obtained Si-enriched Al-Si alloy, purified Si is obtained by precipitation. A glow discharge mass spectrometry analysis revealed that the proposed process can effectively remove the dominant impurities such as Fe, Mn, Ti and V from metallurgical grade Si (98-99% purity). A preliminary electrolysis using Si cells recovered from a commercial photovoltaic module, of which the dominant impurities are Ag, Al and Na, showed that the present process is also applicable for Si recycling from waste photovoltaic modules. (C) The Author(s) 2016. Published by ECS. All rights reserved.