The possibility was investigated of synthesizing Sb-S-containing nanolayers on the silica surface by the method of ion layering, with acetic acid SbCl₃ solutions and gaseous H₂S used as reagents. The layers obtained were analyzed by X-ray photoelectron spectroscopy, X-ray fluorescence microanalysis, spectroscopy of diffuse reflection and transmission in the UV and visible spectral regions, and ellipsometry. Thermally induced transformations of nanolayers were studied in air, and temperature intervals were determined in which sulfamide is oxidized to give Sb(III) and Sb(V) oxides.