We have prepared ultrathin multilayer nanostructural films by a layer-by-layer spin self-assembly method using poly (p-phenylene vinylene) (PPV)/layered silicate and characterized them by contact angle measurement, surface dying technique, UV/ Vis spectroscopy, photoluminescent (PL) spectroscopy, X-ray reflectivity (XRR), and model-fitting. The hybrid ultrathin multilayer film was stepwisely deposited using the electrostatic forces between the cationic PPV precursor and the negatively charged surface of layered silicate, and finally thermally converted to (PPV/Laponite RD)(n) film. The surface coverage of the PPV precursor onto layered silicate and vice versa could be clearly observed using the contact angle measurement and surface dying technique. The continuous increase of UV/Vis absorbance and PL intensity of the films with each bilayer demonstrated the regular and reproducible deposition of this system, and the Kiessig fringes and Bragg peaks in XRR spectra indicated the well-ordered internal structure. (C) 2003 Elsevier B.V. All rights reserved.