Hybrid materials, which combine properties of organic-inorganic materials, are of profound interest owing to their unexpected synergistically derived properties and are considered as innovative advanced materials promising new applications in many fields such as optics, electronics, ionics and mechanics. Inorganic fillers are added to polymers in order to increase some of the properties of the compounds. These hybrid polymeric materials are replacing the pristine polymers due to their higher strength and stiffness. In the present work, studies concerning the preparation of poly (methylmethacrylate) [PMMA] and the nanocomposites PMMA/SiO2, PMMA/TiO2 are reported. These nanocomposite polymers were synthesized by means of free radical polymerization of methylmethacrylate, further "sol-gel" transformation-based hydrolysis and condensation of corresponding alkoxide was used to prepare the inorganic phase during the polymerization process of MMA. Electrolytes were synthesized based on these nanocomposite polymers and have shown superior properties as compared to conventional polymer electrolytes. The nanocomposites and the nanocomposite polymer electrolytes (NPEs) with different lithium salts were investigated through an array of techniques including FTIR and calorimetry along with the electrochemnical and rheological techniques. (c) 2007 Wiley Periodicals, Inc.