The adsorption of different ethoxysilanes on Al was studied. It was established that during polymolecular adsorption of ethoxysilanes from the vapor phase on aluminum the first monolayer is adsorbed irreversibly with adsorption van der Waals bonds between silane molecules and the aluminum surface. The covalent bonding of silanes with the surface (Al-O-Si bonds) occurs in the presence of adsorbed water on the aluminum surface. The presence of a silane monolayer on Al decreases water adsorption on the surface, and inhibits hydration of the oxide metal film. The formation of a negatively charged siloxane film on the aluminum surface inhibits local metal corrosion, and a positively charged layer activates it in chloride containing media. The formation of the surface siloxane polymer by the modification of metals inhibits the metal dissolution under polymer coatings. It is caused by silane chemisorption and negative charging of the metal surface. The presence of negatively charged groups causes difficulties of an electrostatic character for the migration of aggressive ions to the metal surface.