The photochemical stability of the active layer blend for organic solar cells was explored by introducing electron withdrawing cyano groups into the backbone of poly-3-hexylthiophene (P3HT). Random copolymerization of 2-bromo-3-hexyl-5-trimethylstannylthiophene and 2-bromo-3-cyano-5-trimethylstannylthiophene enabled introduction of the cyanogroups along the polythiophene backbone. The percentage of the cyano groups was 10%. The photochemical stability of poly(3-hexylthiophene-co-3-cyanothiophene) (CN-P3HT) was shown to be significantly better than pristine P3HT and the addition of CN-P3HT to P3HT also increased the photochemical stability of the blend. The photochemical stability of bulk heterojunction mixtures of the polymers and their blends with the fullerene phenyl-C61-butyric acid methyl ester (PCBM) were then studied and it was found that PCBM had a significantly more stabilizing effect on P3HT than CN-P3HT and that the stabilization of the bulk heterojunction mixture was dominated by the fullerene. The mixture comprising both fullerene and CN-P3HT, however, demonstrated the highest degree of photochemical stability supporting earlier observations that the stabilizing effects are additive. Finally, the blends were explored in fully printed flexible ITO-free roll coated inverted devices (with an active area of ) using two different back PEDOT:PSS electrode compositions and the operational stability of the devices was studied under ISOS-L-2 conditions. The pure P3HT:PCBM devices were found to be the most stable in operation demonstrating that photochemical stability alone is not necessarily the dominant factor for overall device stability.