Organically modified silicates (ormosils) of two systems were coated on polyethyleneterephthalate (PET) substrates. One was the tetraethoxysilane (TEOS)-vinyltriethoxysilane (VTES) system and the other was the TEOS-tetraisopropyltitanate (TIPT)-VTES system. The reactions among the alkoxides were examined by liquid state 29Si nuclear magnetic resonance (NMR) spectroscopy. The chemical bonds between TEOS and VTES, between TEOS and TIPT, and between VTES and TIPT are shown in the spectra and the reaction schemes are proposed. Vickers hardnesses of the ormosil coatings were obtained by using the models developed by Jonsson and Hogmark, and the theoretical models developed by the authors were valuable to predict the hardness values. The ormosil coatings obtained in the present study were much harder than the hardest transparent plastics, and thus are very useful for hard or protective coatings on organic polymers.