X-ray photoelectron spectroscopy (XPS) was used to monitor the chemical changes resulting from irradiation (> 295 nm) in air of poly(3-hexylthiophene) (P3HT), polymer which is a good candidate for photovoltaic applications. The formation of carbonyl moieties and the stepwise oxidation of sulphur atoms were characterised. The oxidation and the cleavage of the hexyl side-chain was monitored. It is also shown that sulfur was first converted into sulfoxides, then into sulfones and finally into sulfinate esters. The formation of these ultimate degradation products provoked a disruption of π-conjugation in P3HT, leading to diminished visible absorbance. Based on these results, a mechanism of P3HT photooxidation is proposed. Comparison of XPS data with previously reported infrared and UV-visible spectral analysis showed that the information provided by these techniques is completely consistent.