The present work aims to investigate the impact of a low amount of photo-induced silver nanoparticles (0.2 and 0.4 wt.% of Ag NPs) on the stability of acrylate materials (carriers of ester and ether groups) under the combined effect of oxygen and light. Different techniques were implemented to monitor the structural changes at different scales. The determination of the influence of AgNPs required a preliminary investigation of the pure acrylate polymer under the same experimental conditions. The polymer underwent a post-polymerization of the residual vinyl groups and a photo-oxidative degradation. This degradation induced chemical modifications evidenced by infrared spectroscopy and architectural changes resulting from chain scission reactions. These reactions were not only responsible for the steaming of volatile organic compounds, detected by HS-SPME/GC-MS but also for the increase in mesh size controlled by thermoporosimetry. As regards the polymer/Ag NPs composite, the higher the amount of filler dispersed in the matrix, the greater the rate of degradation. This behaviour was due to the photocatalytic effect of Ag NPs, regardless of the loading in nanoparticles. As a result of irradiation, the nanoparticles migrate to the surface of the film and coalesce, thus inducing an increase in size distribution and a gradient structuring as revealed by TEM analysis. The outcomes of this investigation are important for the development of new composite material with new functionalities (antibacterial, optical, conductive properties) for industrial applications as in textile industry.