Low‐bandgap polymers are sensitive to various degradation processes, which strongly decrease their lifetime. The chemical and physical changes occurring in the low‐bandgap polymer with benzodithiophene units poly[4,8‐bis(5‐(2‐ethylhexyl)thiophene‐2‐yl)benzo[1,2‐b:4,5‐b′]dithiophene‐2,6‐diyl‐alt‐(4‐(2‐ethylhexyl)‐3‐fluorothieno[3,4‐b]thiophene‐2‐carboxylate] (PTB7‐Th) and its blend with the fullerene derivative [6,6]‐phenyl‐C71‐butyric acid methyl ester (PC71BM) are followed during irradiation‐induced aging by combination of various characterization methods. The active layer morphology is investigated using atomic force microscopy (AFM) as well as in‐operando grazing incidence small angle X‐ray scattering (GISAXS), indicating morphological alterations and material loss due to chemical modifications. Optical spectroscopy gives insights into these chemical processes which lead to significant absorption losses under ambient conditions. Independent of the energy of the absorbed photons, but only in combination with oxygen, the excitation of the polymer leads to a fatal increase in oxidation probability. Fourier transform infrared (FTIR) data highlight the sensitivity of the conjugated polymer backbone to oxidation, a result of lost conjugation and therefore absorption capability. With combined AFM height and infrared (IR) mapping, the chemical degradation and material loss is confirmed on a nanoscale. Although the chemical structure is seriously damaged, the blend morphology is not undergoing major changes.