This article investigates the modification of a carbon steel surface by benzotriazole (BTA), and the structure and properties of the formed layers. Adsorption was studied by surface analytical methods such as X-ray photoelectron spectroscopy (XPS) and reflecting infrared microscopy (FTIR). It has been established that a polymer-like film containing iron-azole complexes that are 2 nm thick and strongly bonded to the metal is formed on the surface as a result of the azole interacting with a steel surface. This film is capable to inhibit uniform and localized corrosion of steel in neutral aqueous electrolytes containing chloride ions. It is shown that the iron-azole layer located at the interface acts as a promotor of adhesion, increasing the interaction of polymeric coatings with the steel surface. Taking into account these properties, the steel pretreatments can be used for improving the anticorrosion properties of polymeric coatings applied for the protection of steel constructions.