Previously, we found that modification of the membrane surface from polyvinyltrimethylsilane (PVTMS) by treatment with low-temperature plasma induced by low pressure DC discharge leads to a significant increase in gas separation characteristics. To understand the mechanism of this phenomenon, in this article XPS combined with precision etching 10 keV beam of Ar₂₅₀₀⁺ clusters was used for depth profiling of PVTMS spin-coated films before and after DC discharge treatment. The etching craters depths were measured by stylus surface profiler. The average etching rate of the untreated PVTMS film by Ar₂₅₀₀⁺ clusters was defined (230 nm/min). It was found that the low temperature plasma treatment of PVTMS leads to a sharp increase in the oxygen concentration on a surface with a simultaneous decrease in the carbon content. The experimental data obtained indicate also that the treatment of PVTMS film by plasma leads not only to a change in the chemical structure of the surface, but also to the formation of a gradient subsurface layer with a thickness of about 50 nm.