Pre-hydrolysed/condensed tetraethyl orthosilicate (TEOS) was added to a solution of methyl methacrylate (MMA) and 3-methacryloxypropyltrimethoxysilane (MAPTMS), and then copolymerised for various times to study the influence of the latter on the structure of hybrid sol-gel coatings as corrosion protection of aluminium alloy 7075-T6. The reactions taking place during preparation were characterised using real-time Fourier transform infrared spectroscopy, dynamic light scattering and gel permeation chromatography. The solution characteristics were evaluated, using viscosimetry, followed by measurements of thermal stability determined by thermogravimetric analysis. The optimal temperature for the condensation reaction was determined with the help of high-pressure differential scanning calorimetry. Once deposited on 7075-T6 substrates, the coatings were evaluated using a field emission scanning electron microscope coupled to an energy dispersive spectrometer to determine surface morphology, topography, composition and coating thickness. Corrosion properties were tested in dilute Harrison’s solution (3.5 g/L (NH4)2SO4 and 0.5 g/L NaCl) using electrochemical impedance spectroscopy. The copolymerization of MMA and MAPTMS over 4 h was optimal for obtaining 1.4 µm thick coating with superior barrier protection against corrosion attack (|Z10 mHz| ~ 1 GΩ cm2) during three months of exposure to the corrosive medium.