The mechanism of the vapor–gas deposition of vinyltrimethoxysilane (VS) and ethylene glycol (EG) from azeotropic solutions is investigated, which allows a reduction of the evaporation temperature of the components of working mixtures. The need for such studies is associated with the development of a new direction in the technology of vapor–gas deposition of polymer coatings. Methods have been developed for monitoring the chemical composition of working solutions in evaporators using optical spectroscopy, which makes it possible to calculate the partial pressures of vapor-phase components. Based on these studies, compositions of working solutions are proposed that allow the equalization of the partial pressures of the components of working mixtures with a large difference in the boiling point. With the aid of vapor–gas deposition, siloxane coatings on low-carbon steel were obtained, the protective properties of which exceeded the treatment with volatile inhibitors of the adsorption type by two to three orders of magnitude. A new method of vapor–gas deposition of non-volatile powder inhibitors on metals is proposed. Chemical compositions of siloxane coatings were determined using XPS, and mechanisms of interaction of VS with the polymerization promoters ethylene glycol and 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) were proposed.