Organic photovoltaic devices using an electrode of indium tin oxide (ITO) coated with a buffer layer of poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) exposed to controlled humidity during fabrication showed a 65-75% decrease in efficiency and displayed S-shaped J-V curves, changes, which are attributed to different levels of indium and tin migration into the PEDOT:PSS film. A distinct shift in the secondary electron cut-off in the UV Photoelectron spectra (UPS) of ITO/PEDOT:PSS samples exposed to controlled humidity indicate an increase of the dipole at the ITO/PEDOT:PSS interface, which could explain the appearance of S-shaped J-V curves. Additionally, the electron density at low binding energies is reduced for the humidity exposed PEDOT:PSS suggesting a second mechanism for decreased device performance. (C) 2011 Elsevier B.V. All rights reserved.