Hybrid organic-inorganic materials derived from 3-glycidoxypropyltrimethoxylsilane were prepared via two different synthetic routes: (1) the HCl-catalyzed sol-gel approach of silane followed by the lithium perchlorate (LiClO4)/HCl-catalyzed opening of epoxide and (2) the simultaneous gelation of tin/LiClO4-catalyzed silane/ epoxide groups. LiClO4 catalyzed the epoxide polymerization, and its effects on the structures of these hybrid materials were studied by NMR. The structure of the inorganic side was probed by solid-state Si-29 NMR spectroscopy, and the characterizations of the organic side and the chemical processes involved in the different synthetic routes were performed with solid-state cross-polarity/magic-angle-spinning C-13 NMR. The different synthetic routes significantly affected the polymerization behaviors of the organic and inorganic sides in the presence of LiClO4. A larger amount of LiClO4 promoted the opening of epoxide and led to the formation of longer poly(ethylene oxide) chains via the HCl-catalyzed sol-gel approach, whereas in the case of the tin-catalyzed approach, the faster polymerization of the inorganic side hindered the growth of the organic network. The addition of LiClO4 was proven to be without crystalline salt present in the hybrid networks by wide-angle X-ray powder diffraction. Also, the interactions between the ions and hybrid host, examined with Fourier transform infrared and Li-7 proton-decoupled magic-angle-spinning NMR, further demonstrated that extensive ion aggregation existed in these hybrid materials. (C) 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 151-161, 2004.