We have fabricated three kinds of poly(p-phenylene vinylene) (PPV)-layered silicate nanostructures via three different methods. The first is PPV/layered silicate nanocomposite by solution blending, the second is layer-by-layer spin-coated multilayer structure of PPV/layered silicate via simple spin coating and drying, and the third is layer-by-layer spin-assembly multilayer structure using the electrostatic force between the positively charged precursor of PPV and the negative surface of layered silicate. Each sample was characterized by various methods: X-ray diffraction, UV/VIS spectroscopy, photoluminescence spectroscopy, and X-ray reflectivity. We found out that PPV/layered silicate hybrid materials are environmentally stable and nanoscale controllable.