This work focused on the preparation of poly (vinyl alcohol) (PVA)/inorganic composites. Perlite and organically modified montmorillonite (OMMT) were used as the inorganic compounds. (PVA)/inorganic nanocomposite films were prepared by solvent solution method. The morphology, dynamic mechanical property, and the photochemical stability of these films were studied. The reaction pathway between these OMMT and PVA was suggested that the hydrogen bonding and hydrophobic interactions contributed to the preparation. The obtained new materials have different thermal, mechanical, and photochemical stability from other single components.