Multilayer nanostructural thin films through a layer-by-layer spin self-assembly method were prepared using poly(p-phenylene vinylene)/montmorillonite. Sodium montmorillonite particles exfoliated into single sheets and cationic PPV precursor and such anionic MMT plates were spin self-assembled by electrostatic attraction. Self-assembled MMT layers blocked the penetration of oxygen and moisture and they reduced the photo-oxidation of the emitting material. Spin self-assembled films showed higher environmental stability and luminescence, and their PL spectra were somewhat different from that of bulk PPV films.