In the present research, groups of nanolayered structures and nanohybrids based on organic green dyes and inorganic species are designated to act as fillers for PVA to induce new optical sites and increase its thermal stability through producing polymeric nanocomposites. In this trend, different percentages of naphthol green B were intercalated as pillars inside the Zn-Al nanolayered structures to form green organic-inorganic nanohybrids. The two-dimensional green nanohybrids were identified by X-ray diffraction, TEM and SEM. According to the thermal analyses, the nanohybrid, which has the highest amount of green dyes, was used for modifying the PVA through two series. In the first series, three nanocomposites were prepared depending on the green nanohybrid as prepared. In the second series, the yellow nanohybrid, which was produced from the green nanohybrid by thermal treatment, was used to produce another three nanocomposites. The optical properties revealed that the polymeric nanocomposites depending on green nanohybrids became optical-active in UV and visible regions because the energy band gap decreased to 2.2 eV. In addition, the energy band gap of the nanocomposites which depended on yellow nanohybrids was 2.5 eV. The thermal analyses indicated that the polymeric nanocomposites are thermally more stable than that of the original PVA. Finally, the dual functionality of organic-inorganic nanohybrids that were produced from the confinement of organic dyes and the thermal stability of inorganic species converted the non-optical PVA to optical-active polymer in a wide range with high thermal stability.