This study reports the effect of light on PLA/ZnO nanocomposites films produced by melt-extrusion. The attention focused on the discrimination between the photocatalytic degradation of PLA provoked by ZnO and the UV screening effect of the ZnO nanoparticles. The chemical modifications of PLA induced by UV light irradiation were analyzed using infrared spectroscopy and completed through the analysis of the low-molecular-weight photoproducts using 1C and SPME and the characterization of chain scissions with SEC. A comprehensive mechanism for the photooxidation of PLA was then proposed. The results indicated that the photocatalytic activity of ZnO nanoparticles induces the oxidation or PIA. Because ZnO limits the penetration of light inside the samples, this effect mainly concerns the first micrometers at the surface of the exposed samples. Cross-sectional analysis using micro-1R and ATR-IR spectroscopies was performed to highlight the degradation profile in the PLA/ZnO nanocomposites.