The surface free energy and acid-base characteristics of polyethylene coatings formed on steel in the presence of primary aromatic amines (PAAs) were investigated. PAAs were shown to interact with steel by a donor-acceptor mechanism. An increase in the coating adhesion is realized through chemical and physical bond formation between an adhesive and a substrate with the help of the PAA. The free surface energy of the contact-to-metal side of these coatings modified with PAA was shown to grow in parallel with the increase in adhesion. The results correlate with the data on polyethylene surface wetting with nonionic surfactants. Acid-base interactions were found to exert primary control over polyethylene's adhesion to steel.