The development of methods for producing silicon and materials based on it with controllable morphology and composition of microimpurities is a challenging problem, since such materials are widely used in modern microelectronics and power engineering. In this work, the influence of the substrate material and the parameters of silicon electrodeposition from a low-melting low-fluoride LiCl–KCl–CsCl melt with a K2SiF6 addition at a temperature of 545°C on the morphology of the deposit is studied. To determine the range of electrodeposition parameters, the regularities in the cathodic process in this melt are studied on glassy carbon, molybdenum, and nickel using cyclic voltammetry and square-wave voltammetry. This process is shown not to be electrochemically reversible on all the substrates and to proceed in two stages. Varying the electrodeposition parameters, three silicon deposits are formed for each of the substrates. On glassy carbon, a silicon film in the form of spherical dendrites uniformly distributed over the electrode surface and silicon fibers are deposited depending on the electrodeposition conditions. On molybdenum, silicon is deposited in the form of ordered dendrites, fibers, and a continuous coating consisting of spherical particles, as in the case of glassy carbon, depending on the electrolysis conditions. On nickel electrodes, nickel silicides and also silicon dendrites and fibers are deposited.