Poly (ethylene oxide) (PEO), polyvinylpyrrolidone (PVP), methyl cellulose (Mcel), poly [oligo(ethylene glycol)-oxalate] (POEGO), poly[oxymethylene-(oxyethylene)] (POMOE), and poly[bis-(methoxyethoxyethoxy)phosphazene] (MEEP) were intercalated into hectorite. The intercalated hectorites were characterized by powder X-ray diffraction (XRD), thermogravimetric analysis (TGA) and infra-red spectroscopy. The interlayer expansion depended on the amount of polymer added as well as on its dimension. The polymer-intercalated materials exhibited higher thermal stability when compared to the bulk polymers.