Abstract We present a study of dark air-exposure degradation of organic solar cells based on photoactive blends of the conjugated polymer, poly[2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylene vinylene] (MDMO-PPV) with [6,6]-phenyl C61-butyric acid methyl ester (PCBM). Photovoltaic devices were fabricated on indium tin oxide (ITO) glass with or without a layer of poly (3,4-ethylenedioxythiophene):poly(4-styrene sulfonate) (PEDOT:PSS), and were studied without encapsulation. Photovoltaic performance characteristics were measured as a function of time for different ambient conditions (under white light irradiation and in the dark, and under air, dry oxygen and humid nitrogen atmospheres). It was found that a key cause of degradation under air exposure is light independent and results from water adsorption by the hygroscopic PEDOT:PSS layer. Measurements of the charge mobility and hole injection after air exposure showed that the degradation increases the resistance of the PEDOT:PSS/blend layer interface.