A new electrolytic production process for solar-grade Si has been proposed utilizing liquid Si-Zn alloy cathode in molten CaCl2. To establish this process, the behavior of liquid Zn metal in molten CaCl2 at 1123 K was investigated. Evaporation of Zn metal was largely suppressed by immersion in the molten salt, which enabled the use of a Zn electrode despite its high vapor pressure. Cyclic voltammetry results suggested that the reduction of SiO2 on a Zn cathode proceeded at a more negative than 1.45 V vs. Ca2+/Ca. After potentiostatic electrolysis at 0.9 V, Si particles with sizes of 2-30 mu m were precipitated in the solidified Zn matrix by a slow cooling process. The rate-determining step for electrochemical reduction of SiO2 on the Zn cathode was discussed on the basis of a measurement of the alloying rate between solid Si and liquid Zn. (C) The Author(s) 2017. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse of the work in any medium, provided the original work is properly cited. All rights reserved.