Electron microscopy has been used to study the degradation of organic solar cells when exposed to humid air. Devices with various different combinations of commonly used organic solar cell hole transport layers and cathode materials have been investigated. In this way the ingress of water and the effect it has on devices could be studied. It was found that calcium and aluminum in the cathode both react with water, causing voids and delamination within the device. The use of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) was found to increase the degradation by easing water ingress into the device. Replacing these materials removed these degradation features. © 2015 The Authors. Journal of Polymer Science Part B: Polymer Physics published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 216-224.