Polymer-based solar cells (PSC) represent a promising technology in the field of photovoltaics, although they still suffer from poor environmental stability. Poly(3-hexylthiophene) (P3HT) is one of the most commonly employed electron-donor materials for the preparation of the photo-active layer of PSC and it is known to undergo degradation when exposed to light. In this work, the degradation of P3HT was studied by irradiating polymer films by means of simulated sunlight. The results of this study highlighted a remarkable instability of P3HT. Substantial modifications of the infrared as well as of the UV-Vis spectra of the polymer were reported and a degradation pathway was suggested, in agreement with recent literature results. In order to stabilize the structure, two additives were evaluated namely a standard Hindered Amine Light Stabilizer (HALS) and Multi-Walled Carbon Nanotubes (MWCNT). The addition of MWCNT appeared to significantly reduce the rate of degradation.