The stability of conjugated organic materials under electron transport is of great importance for the lifetime of devices such as polymer light-emitting diodes (PLEDs). Here, the modification of thin films of poly(3,4- ethylenedioxythiophene) oxidized with poly(4-styrenesulfonate) (known as PEDOT-PSS, often used in the fabrication of PLEDs) by low-energy electrons has been studied using X-ray photo-electron spectroscopy. Thin films of PSSH and molecular solid films of EDOT molecules also have been studied. We find that electrons with kinetic energies as low as 3 eV result in significant modification of the chemical structure of the materials. For thin films of PSSH, the electron bombardment leads to a strong loss of oxygen and a smaller loss of sulfur. In addition, a large amount of the sulfur atoms that remain in the films exhibits a different binding energy because of scissions of the bonds to oxygen atoms. For condensed molecular solid films of EDOT molecules, we find that the carbon atoms bonded to oxygen react and form additional bonds, as evidenced by a new component in the C(1s) peak at a higher binding energy. In the PEDOT-PSS blend, we find both effects. The importance of these observations for light-emitting diodes incorporating PEDOT-PSS films is discussed. This work demonstrates that the combination of in situ low-energy electron bombardment in combination with photo-electron spectroscopy is a powerful method to simulate and study certain processes, associated with low-energy electrons, occurring in organic based devices, which cannot be studied directly otherwise. © 2002 Elsevier Science B.V. All rights reserved.