Polymer–clay nanocomposites of poly(ethylene oxide)/Na-montmorillonite (PEO/MMT) and PEO/organo-modified bentonite (B34) systems prepared via solution intercalation and melt intercalation have been compared by X-ray diffraction and Fourier transform infrared (FTIR) analysis. The gallery size of solution-intercalated hybrids in both PEO/MMT and PEO/B34 systems increases with PEO content up to a plateau level at 15%. However, the gallery size of melt-intercalated PEO/MMT and PEO/B34 hybrid remains the same regardless of the PEO concentration. FTIR analysis shows no difference in spectrum of samples prepared by solution intercalation compared to melt intercalation. The PEO conformation in the PEO/clay intercalated hybrids is concluded to be a distorted helical structure.