Transparent and colorless nanocomposite coatings were prepared from a hybrid organic–inorganic matrix and several inorganic nanofillers. The products are characterized by a high degree of self-assembling of the matrix which was prepared from an epoxy-functional
organosilicon precursor and an oligomeric diamine. Unmodified and chemically modified montmorillonite, bentonite, laponite, and colloidal silica were used as nanofillers, differing in shape, size, and origin. The nanoadditive concentration in coatings was always 0.5wt%. Solid-state NMR (13C and 29Si CP/MAS) spectroscopy was used for estimation of polyaddition and polycondensation degree in the polymer matrix in order to evaluate its structure changes caused by interaction with the nanoadditives. The influence of the kind of additive on the dynamic mechanical properties, gas permeability, and surface properties (topography, roughness) is discussed.