In this paper, we have sought to determine if a reflective silver coating layer could prevent the degradation of a silver/acrylate polymer assembly and the loss of its optical property in an environment simulating sunlight. For this purpose, a multiscale approach from micro(nano) scale to macroscopic scale was applied. The overcomes of this investigation revealed that the metallic coating did not act as a barrier against photooxidation of the polymer matrix and silver nanoparticles, on contrary, catalysed the degradation process. The multiscale approach showed that not only the matrix underwent structural and architectural changes with the formation of oxidative products and volatile compounds due to chain scission reaction, but also the alteration of the metallic layer with the formation of defects at its surface, evidenced by optical and atomic force microscopy. An original approach using photo-DSC allowed to monitor the thermo-optical properties of the material. It pointed out the loss of the optical properties of the silver/polymer assembly during irradiation that was linked to the degradation of the acrylate polymer.