The influence of layered double hydroxides (LDHs) on the photooxidation of polypropylene (PP)/LDH nanocomposites was studied under irradiation at long wavelengths (λ > 300 nm, 60 °C and in the presence of oxygen). The influence of hybrid LDHs containing different divalent cations (Mg, Zn or both Mg and Zn) on the photooxidation mechanism of PP and on the rates of oxidation of the matrix was characterised based on infrared analysis. The presence of LDHs modifies the photoproducts accumulating in the PP and the rates of oxidation of PP were changed depending on the divalent cations in the LDH layers. Whereas natural clays, such as montmorillonite (MMt), can lead to a faster degradation of the materials, LDHs (Zn2-Al-DS, for example) appear to have no inductive effect on polymer oxidation.