Due to its abundance in nature as well as its properties, silicon is one of the most demanded materials in various industry areas. Currently, metallurgical silicon is obtained by carbothermic reduction of quartz. In order to obtain solar grade silicon, the last should be treated by hydrochlorination and multiple chlorination. This brief review presents an analysis of alternative methods for obtaining silicon by electrolysis of molten salts. The factors that determine the choice of the composition of molten salts, typical silicon deposits obtained by electrolysis of molten salts are shown. An assessment of the results and prospects for further use of electrodeposited silicon in lithium-ion power sources and representative test results on the use of electrolytic silicon for solar energy conversion devices were presented. The problems that need to be solved for the practical implementation of methods for the electrolytic production of silicon samples suitable for new devices and materials for energy conversion and storage are noted.