A poly(methyl methacrylate) (PMMA)-clay hybrid resin was prepared via bulk polymerization methyl methacrylate monomer in the presence of montmorillonite intercalated with an ammonium salt of dctadecylamine. The products were characterized by infrared spectroscopy, X-ray diffraction, pyrolysis gas chromatography, and transmission electron microscopy. Results confirm that the resin is intercalated with PMMA molecules. The layer spacing of montmorillonite are enlarged, whereas the silicate layers are homogeneously dispersed individually. When the PMMA-clay hybrid was blended with plasticized poly(vinyl chloride), the resulting composite exhibited excellent barrier property in preventing the plastizer's migration from the inner matrix to the surface of the product. This is presumably caused by barrier property of the silicate layers dispersed in the composite.