The relaxation behavior of poly( ethylene oxide) (PEG), intercalated in montmorillonite, a naturally occurring mica-type silicate, was studied by differential scanning calorimetry (DSC) and thermally stimulated dielectric depolarization(or thermally stimulated current, TSC). The materials were synthesized by melt or solution-mediated intercalation. In both intercalates, the PEO chains were confined to ca. 0.8-nm galleries between the silicate layers. The solution intercalate contained a fraction of unintercalated PEO chains which exhibited a weak and depressed PEO melting endotherm in DSC. In contrast, the melt intercalate was "starved" such that almost all the PEO chains were effectively intercalated. For these melt intercalates, no thermal events were detected by DSC. TSC thermal sampling technique was used to examine the glass transition regions and to estimate the extent of cooperativity of chain motions. The motions of the intercalated PEO chains are inherently noncooperative relative to the cooperative T-g motions in the amorphous portion of the bulk polymer. This is presumably due to the strong confining effect of the silicate layers on the relaxations of the intercalated polymer.