In our research, we investigate a method of nanocomposite preparation based on self-organization processes due to the formation of a thick polymerizable shell around each nanoparticle and allowing one to get a uniform optical quasihomogeneous material. In the present work, we will study changes of the optical and structural properties of polymer nanocomposites. An UV-curable active matrix was polymerized on the surface of SiO2 nanoparticles. The set of structural modifications of polymeric nanocomposites were observed by using ASM, SEM, light scattering, and water sorption and by measuring the Brinell hardness. Hypotheses concerning the participation of nanoparticles in the photopolymerization are discussed.