Solvent additives such as diiodooctane (DIO) are becoming ubiquitous in processing high performance organic photovoltaic (OPV) active layers. Here, we investigate the effects of DIO on the long-term stability of the active layer by studying the photodegradation under ambient white light illumination of the polymer PTB7-Th in pure polymer thin films and in blend films with PC71BM. Using X-ray fluorescence, we directly detect iodine in the active layer films, indicating the presence of residual DIO after casting from solution. Additionally, we show that this residual DIO dramatically decreases the photostability of the active layer. Structural changes in the films upon illumination are probed with grazing-incidence wide-angle X-ray scattering...