We report here the synthesis and characterization of a series of p-type copolymers, which combine a fluorinated quinoxaline (FQ) acceptor unit either with a differently substituted benzodithiophene (BDT) or an unsubstituted thieno[3,2-b]thiophene (TT). The effect of the structural modifications on the photochemical stability of the resulting films is investigated and then correlated with the photovoltaic performance and lifetime measurements of corresponding photovolatic devices. To this end, we firstly studied the intrinsic stability of each polymer film by monitoring the UV-vis absorption decay, under simulated sunlight, as a function of ageing time. Bulk heterojunction solar cells, based on these polymers as donor materials, were fabricated and tested. Beside the initial values, we monitored the photovoltaic performance during prolonged light soaking in order to evaluate and compare the photostability of more complex systems such as working solar cells.