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 (∼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.