The silicon electrodeposition from the KF-KCl-(10 mol%) K2SiF6 melt at 943-1103 K has been studied. The polycrystalline continuous single-phase silicon coatings (similar to 99.9 wt% Si) have been obtained on the graphite, glassy carbon, silver, and tungsten substrates. The Raman spectroscopic study of the Si/C and Si/Ag interfaces has proved an absence of the intermediate phases. Two phases (Si and Ni2Si) were formed during the silicon electrodeposition on nickel. (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.