A new type of organic inorganic hybrid electrolyte has been developed by a sol gel process through the reaction of cyanuric chloride with poly(oxyalkylene) diamine and 3-isocyanatepropyltriethoxysilane, followed by co-condensation of 2-[methoxy(polyethyleneoxy)propyl]trimethoxysilane. A maximum ionic conductivity of 1.0 x 10(-4) Scm(-1) at 30 degrees C has been achieved with the solid hybrid electrolyte. The results of solid-state NMR not only confirm the structural framework of the hybrids, but also provide a microscopic view of the effects of salt concentrations on the dynamic behavior of the polymer chains. The hybrid materials are blended with PVdF-HFP to form the blend hybrid membrane, followed by plasticization with various electrolyte solvents, with the purpose of increasing ionic conductivity. The plasticized blend hybrid electrolyte exhibits a maximum room temperature ionic conductivity of 8.8 x 10 (-3) Scm(-1). Such a high ionic conductivity allows it as a potential candidate for applications in lithium ion batteries. (C) 2012 Elsevier Ltd. All rights reserved.