We report on self-assembly of polymer and molybdenum oxide chains into a new class of lamellar hybrid materials. Aqueous ammonium molybdate and polyvinyl alcohol (PVA) or carboxymethyl cellulose (CMC) were used as the starting materials. Ammonium molybdate was hydrolyzed into layered molybdenum oxide under acidified conditions. The organic polymer chains and the inorganic molybdenum oxide layers self-assemble and pack into new hybrid composites. Scanning electron microscope (SEM) images and polarized microscopy show that these two new materials have typical lamellar structure. Transmission electron microscope (TEM) images show that the layer thickness is about 100 run. X-ray diffraction (XRD) data confirm the formation of inorganic molybdenum oxide. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) data gave thermal behavior of these composites. The mechanism of this hybrid reaction and the templating function of polymers were discussed in this paper. A special entropy effect was discovered when polymer was used as guest species. This entropy effect makes polymers preferential candidates as guest species rather than small molecules when fabricating organic/inorganic layered hybrid materials. We believe that this opens a new way to create organic/inorganic hybrid superstructures. (C) 2008 Elsevier Inc. All rights reserved.