Low thermal and mechanical stability and the lack of ultraviolet (UV) shielding ability have restricted the practical applications of poly(vinyl chloride) (PVC). In this study, we tried to use a hybrid nanostructure containing α-MnO2 nanorods and layered double hydroxides (LDHs) to modify PVC's features. LDH and α-MnO2 nanorods were first modified with bio-safe molecules to make them compatible with the PVC matrix. Then, three different weight percentages of the resulting nanohybrid (5, 10 and 15 wt%) were inserted in the PVC. The prepared nanocomposite films were identified via numerous analyses. The thermal stability and mechanical strength of the resulting nanocomposite films were examined. UV-visible absorption spectra showed enhanced absorption for the nanocomposites as compared to the pure PVC. The absorption was highly affected by enhancing the nanohybrid content. To evaluate the ability of the resulting nanocomposite films to attenuate ultraviolet (UV) irradiations, these nanocomposites were applied as a shield to prevent methylene blue (MB) dye photodegradation. The results show that when PVC/M-MnO2@D-LDH nanocomposite 15 wt% was used as the shield, the photodegradation rate of MB was dramatically diminished. Consequently, the proposed nanocomposite films, which were prepared via a green route, could be suitable for food, drug and many other packaging applications.