The present work was devoted to the photostability of two homopolymers, resulting from the polymerization of acrylate monomers used as components of recording materials. This study was undertaken in conditions simulating solar light. The objective was to identify the key elements specific of the degradation of each polymer. This approach passed through the understanding of the chemical modifications of the polymer matrix and therefore through the elucidation of the mechanism of degradation. Photo-IR experiments and GC–MS analysis were performed to identify the organic volatile compounds stemming from the photo-oxidation of each homopolymers. A new methodology based on the photo-purge-trap-GC–MS was implemented to have a better insight of the elucidation of the pathways of degradation.