We present two co-polymer families; one based on a thiophene-quinoxaline unit and one on a thiophene-pyrido pyrazine unit. Co-polymerization of these monomers with thiophene-hexylthiophene was performed to create polymers with an optical absorption that fully covers the visible part of the solar spectrum with the aim to enhance the solar cell performances of these polymers. We have also studied how increasing the fraction of thiophene-hexylthiophene affects the photo-oxidative stability of these polymers. Thiophene-pyrido pyrazine solar cells displayed increased device efficiency upon addition of the thiophene-hexylthiophene and, in addition, the stability is retained upon inclusion of these units. In contrast, we found that for the thiophene-quinoxaline based co-polymer, both device efficiency and stability decreased with increasing thiophene-hexylthiophene fraction. Moreover, our results indicate that the photo-oxidative stability of the thiophene-quinoxaline co-polymer is independent of the polymer molecular weight as well as of the film thickness.