A crosslinked polyether network was prepared from poly(ethylene glycol) diglycidyl ether (PEGDE) cured with poly(propylene oxide) polyamine. Significant interactions between ions and polymer host have been observed for the crosslinked polyether network in the presence of LiClO4 by means of FT-IR, DSC, TGA, and Li-7 MAS solid-state NMR. Thermal stability and ionic conductivity of these complexes were also investigated by TGA and AC impedance measurements. The results of FT-IR, DSC, TGA and Li-7 MAS solid-state NMR measurements indicate the formation of different types of complexes through the interaction of ions with different coordination sites of polymer electrolyte networks. The dependence of ionic conductivity was investigated as a function of temperature, LiClO4 concentration and the molecular weight of polyether curing agents. It is observed that the behavior of ion transport follows the empirical Vogel - Tamman - Fulcher (VTF) type relationship for all the samples, implying the diffusion of charge carrier is assisted by the segmental motions of polymer chains. Moreover, the conductivity is also correlated with the interactions between ions and polymer host, and the maximum ionic conductivity occurs at the LiClO4 concentration of [O]/[Li+] = 15. (C) 2003 Elsevier Science Ltd. All rights reserved.