Abstract A tri-functional polyhedral oligomeric silsesquioxane (POSS) based silane precursor R x R y R z (SiO 3/2) n ( x + y + z = n = 6, 8, 10, ….) bearing 3-(N-(3-triethoxysilylpropyl)ureido)propyl, isooctyl and perfluoropropyl groups was synthesized and investigated as corrosion protective coating for AA 2024 alloy. Infrared reflection-absorption (IR RA) combined with X-ray photoelectron spectroscopy and atomic force microscopy provided information about partial self-assembling of coatings having a fluorine enriched upper layer with a low surface energy ( γ tot = 12.37 mN/m). The structural changes that accompanied corrosion produced under chronocoulometrical conditions were assessed from ex-situ IR RA spectra. A new band at 1690–1700 cm − 1 appeared above the corrosion potential, and was assigned to the formation of amidonium ions and consequent relaxation of urea–urea associations.