Direct infrared spectroscopic evidence has been obtained for photodoping of high mobility regioregular poly(3-alkylthiophene) and poly[2,5-bis(3-alkyllthiophen-2-yl) thieno (3,2-b)thiophene] with the attendant formation of hydroxide counter-ions. This reveals the central role of dissolved water, explains the key features of degradation of the electrical characteristics of organic semiconductors in the ambient (see figure), and points to possible strategies to further improve their stability.