The mechanism of iron corrosion protection by thin siloxane films was clarified. Quartz crystal microbalance technique (QCM) was applied to control the vapour phase deposition of alkoxysilanes and the formation of thin siloxane films. It was shown that the addition of water vapour increased the thickness of the grafted siloxane films. Crystal-like films spontaneously grow to 10–16 monolayers at 100% RH of Ar flow due to the catalytic effect of the surface. X-ray photoelectron (XPS) and Auger spectroscopies analysed the thin siloxane films and Scanning Kelvin Probe (SKP) showed the formation of iron-siloxane bonds passivating the iron surface. The films showed high hydrophobicity and corrosion inhibition in humid air contaminated by sulphur dioxide. Thick films were less ordered, hydrophilic and accelerated the corrosion of iron. For corrosion protection, the presence of oxygen in the atmosphere is extremely important. In a wet Ar atmosphere, contaminated by sulphur dioxide, the surfaces are not stable and quickly corroded. Oxygen adsorption stabilizes the surface oxide film that correspondingly preserves the anchoring iron-siloxane bonds and enables corrosion protection by the coating. © 2021 by the authors.