Abstract <p>Equipment in the chemical industry is susceptible to corrosion due to the low corrosion resistance of carbon steel in aggressive environments. Polymer coatings are used to enhance the corrosion resistance of equipment. The adhesive interaction strength between the polymers (adhesives) and the steel (substrate) is determined by the adhesion mechanism. This work explores adhesive interaction between an adhesive (polyethylene terephthalate, poly(methyl methacrylate), polystyrene, or polypropylene) and a substrate (steel St3) experimentally and theoretically. Experiments served to determine the acid–base surface properties of the adhesive and substrate using the Berger and van Oss–Chaudhury–Good methods. Polyethylene terephthalate, poly(methyl methacrylate), and polystyrene were found to have basic properties, while polypropylene and the substrate had acidic properties. The theoretical method consisted in the quantum-chemical modeling of adhesive interaction between the chosen adhesives and substrate. α-Fe₂O₃ was regarded as the substrate surface model. The adhesive interaction mechanism and energy characteristics of adhesive–α-Fe₂O₃ systems were determined by the B3LYP-GD3/6-31G(d,p) method. The adhesive interaction strength was assessed via the adhesion energy. The reactive sites in the adhesive–α-Fe₂O₃ systems were found to be the surface functional groups of the adhesives, the presence of which helps strong adhesion to the substrate surface. The strongest interaction was in the systems formed via the carbonyl oxygen atom. The experimental and calculated data are well consistent.</p>