A new method was developed for the covalent incorporation of acrylate polymers into a silica network in order to form monolithic highly transparent hybrid materials that present excellent mechanical properties with no surface cracking. Glycidyl methacrylate (GMA) and 2-hydroxyl ethyl methacrylate (HEMA) were the two acrylate monomers used to form the poly(HEMA-GMA-silica) hybrids which showed better mechanical properties compared to commercial Plexiglas^TM. GMA as a co-monomer facilitates the removal of almost all of the low molecular weight byproducts formed during the sol-gel reactions and also prevents the further condensation of the free silanol groups during storage and/or polymerization of the vinyl monomers, by capping the free hydroxyls of the silanol groups. The mechanical properties of poly(HEMA-GMA-Silica) hybrids were evaluated by compression tests whereas NIR spectroscopy was used to monitor the capping process and ensure that the reaction reaches completion. Moreover, a covalent incorporation of polyaniline in these hybrid materials has also been achieved. The electric conductivity and electroactivity of the materials were investigated. The results indicate that these materials can have various potential applications in areas where high modulus, high compressive strength, conductivity, electroactivity and changes of color are desirable.