A synthesis route for preparing highly conductive solid organic-inorganic hybrid electrolytes has been developed by using cyanuric chloride as the coupling core to react with diamino-terminated poly(oxyalkylene) triblock copolymers, followed by cross-linking with an epoxy alkoxysilane 3-glycidyloxypropyl trimethoxysilane via a sol-gel process The present hybrid electrolyte with a [O]/[Li] I ratio of 32 was found to be the most conductive, reaching a maximum lithium ion conductivity of 6.8 x 10(-5) Scm(-1) at 30 degrees C The Li-ion mobility was determined from (7)Li static NMR line width measurements and correlated with their ionic conductivities. The onset of (7)Li line narrowing was closely related to the T(g) of the hybrid electrolytes as measured by DSC experiments Thus, the motions of the lithium cations are strongly coupled with the segmental motion of the polymer chains, which is in line with the Vogel-Tamman-Fulcher behavior as observed in ionic conductivity (C) 2010 Elsevier Ltd. All rights reserved.