The chemical degradation of the Poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]] or ‘ PTB7’ has been studied using X-ray Photoelectron Spectroscopy (XPS). This material system appears to be intrinsically unstable especially when illuminated in air and XPS studies confirm the rapid photo-degradation is related to changes in chemical structure of the polymer. In particular, XPS spectra show an initial reduction in relative C-C intensity, suggests loss of the alkoxy side chains. This is followed by a dramatic increase in the level of oxygen-bonded species, especially C-O at ~286.5 eV and C(=O)O at 289.2 eV, indicative of COOH and OH group formation, and oxidation of S. The XPS results support the view that using processing additives reduces the chemical stability of the polymer and provides insight into strategies to improve molecular design to ensure higher chemical stability.