Due to the possibility of controlling composition and morphology, one of the promising methods for obtaining silicon and its materials is the electrolysis of molten salts. However, this requires data on the influence of various factors on the kinetics of silicon electrodeposition. In this work, an effect of the cathode substrate material on the kinetics of electroreduction of silicon ions in a low-fluoride melt (wt %) 57KCl–43CsCl with the addition of 2.8 wt % K2SiF6 at a temperature of 730°C was studied by cyclic voltammetry and chronoamperometry. Interacting and indifferent materials for silicon were chosen as substrates: glassy carbon, silver, and nickel. On the glassy carbon electrode, the electroreduction of silicon ions proceeds in the potential region more negative than –0.05 V, on the silver electrode, more negative than 0.05 V, and on the nickel electrode, more negative than 0.40 V relative to the potential of the silicon quasi-reference electrode. For all the studied substrates, a cathode process is observed, which is not electrochemically reversible. In this case, according to chronoamperometry measurements, the stage of nucleation of a new phase at the cathode does not affect the kinetics of the process under study. Presumably, in the case of glassy carbon and silver, irreversibility can be caused by a delayed discharge, while silicon electrodeposition on a nickel electrode is accompanied by the formation of nickel silicides. From the voltammetric and chronoamperometric dependences, the diffusion coefficient of silicon ions to the glassy carbon electrode was estimated, the values of which were 1.5 · 10–5 and 1.2 · 10–5 cm2/s, respectively.