Coatings based on organic-inorganic hybrids may effectively improve the resistance of metals/alloys against corrosion. In this work the protection ability of a coating based on (3-mercaptopropyl)trimethoxysilane (MPTMS) deposited on the well-known aluminium AA 2024 alloy is studied. The hydrolysis and condensation reactions in the initial sol and the structure of thermally treated protective MPTMS coatings is studied using infrared absorbance spectroscopy. In addition, the structure of coatings is investigated using infrared reflection-absorption (IR RA) spectroscopy. Several physical properties of prepared coatings such as contact angles, surface energy and thickness are reported. The corrosion protection ability of once, twice and three times deposited MPTMS coatings is studied using potentiodynamic polarisation measurements. Finally, possible morphological changes at different potentials of interest are investigated using in situ electrochemical AFM.