Silicon is one of the promising anode materials for lithium-ion batteries with enhanced performance. However, the degradation of silicon during lithiation/delithiation is still the main problem that prevents it commercial use as electrodes. In this work the behavior of a silicon film of about 5–6 µm thick electrodeposited from LiCl-KCl-CsCl-K2SiF6 melt on glassy carbon was studied during its lithiation and delithiation, the film being a part of the anode half-cell of a lithium-ion battery.