Currently, research is being actively conducted aimed at developing materials and devices for obtaining and storing energy from renewable sources. In particular, attention is paid to the conversion of solar energy with a view to its subsequent storage in lithium-ion current sources or hydrogen storage devices. In this regard, the possibility of electrochemical synthesis of photoelectroactive thin silicon films on glassy carbon from the low-melting LiCl-KCl-CsCl-K2SiF6 electrolyte at a temperature of 540 °C was studied in this article. Experimental samples of thin silicon films were obtained from the studied electrolyte depending on the electrolysis parameters; their morphology and elemental composition have been studied by means of scanning electron microscopy and energy-dispersive X-ray analysis. The pulsed mode of electrodeposition of the densest film was chosen, including: an anode treatment of the surface of the working electrode at a current density of 14.3 mA/cm2 during 5 s, after which pulsed electrolysis was carried out at a cathode current density of 28.5 mA/cm2 for 30 min with periodic current interruptions. The photoelectric effect of obtained silicon film was studied. A relatively high photosensitivity of the sample was shown due to an increased specific surface area and its energy inhomogeneity. Then, the base properties of the obtained sample were determined by means of atomic emission spectroscopy, visual photoelectron microscopy with plasma treatment of the sample with argon, laser atomic emission spectrometry, and atomic force electron microscopy.