Bis(ureapropyl)triethoxysilane bis(propyl)-terminated-polydimethylsiloxane 1000 (PDMSU), an organic−inorganic hybrid, diluted in either EtOH or a mixture of EtOH−PrOH, was used in thin film form (<200 nm) to inhibit the corrosion of AA 2024 alloy. Potentiodynamic, time-dependent cyclovoltammetric measurements and salt spray tests showed that the corrosion inhibition of the latter was 10 times higher than that of the former films. This was correlated with the higher degree of hydrolysis and the formation of more open polyhedral silsesquioxane species (T2) in the bulk heat-treated PDMSU/EtOH−PrOH xerogels (29Si NMR spectra). The structure of the coatings deposited on AA 2024 Al alloy was deduced from the infrared reflection−absorption (IR RA) spectra, which revealed more extensive urea−urea interactions and more efficient silane−Al interface bonding for the PDMSU/EtOH−PrOH coatings with higher corrosion inhibition. Ex situ IR RA potentiodynamic spectroelectrochemical measurements of PDMSU coatings revealed that their degradation did not proceed via the formation of silanol groups and consequent hydration of the coatings but that they decomposed above E corr by forming fragments composed of −CH2− segments in an all-trans conformation.