Despite tremendous advances in improving the efficiency of organic solar cells above 14%, the environmental stability of such devices remains an essential and widely inadequately addressed challenge. Understanding the underlying principles of device degradation is a critical step toward further development and commercialization of organic photovoltaics. Herein, we report on the effect of oxygen exposure on the operation and degradation of highly efficient PffBT4T-2OD:PC₇₁BM photovoltaic devices. Ultrafast pump-probe transient absorption (TA) measurements and ultrasensitive photothermal deflection spectroscopy (PDS) in combination with field-effect transistors suggest that oxygen-induced doping of the active layer is responsible for the severe degradation of the photovoltaic performance. We find that light exposure further accelerates this effect without causing photo-oxidation of the materials.