Interfacial interaction of poly(ethylene) oxide (PEO) and Li-Al-MCM-41 were studied by 13C, 7 Li and 27Al solid state MAS NMR. In 27Al spectroscopy, it is found that Al in Li-Al-MCM-41 is in tetrahedral position, and generating AlO4 - . 7 Li spectroscopy confirmed that Li+ electrostaticly interacted with AlO4 - in the framework of Li-Al-MCM-41. When PEO was combined with Li-Al-MCM-41 by melt intercalation technique, the interaction of PEO oxygen-bridging atom with Li+ was interpreted from 13C CP/MAS NMR spectroscopy in which case, the PEO peaks shifted downfield by ca. 2 ppm. A smaller linewidth of 13C CP/MAS NMR of PEO/Al-MCM-41 compared to free PEO suggested that PEO segments were distributed in preferred orientations, presumably in the pore channel of MCM-41. A distinct structural feature of the nanocomposite was shown by 7 Li and 13CP/MAS NMR of PEO/Li-Al-MCM-41 in comparison to Li-MCM-41. The results show that the presence Li+ in Li-Al-MCM-41 does not produce any significant peak shifts in the 7 Li spectra suggesting that Li+ was strongly interacted with AlO4 - .