The polymer electrolyte distribution in PEMFC electrodes plays an important role for the catalyst utilization and various transport processes in the electrode. Moreover, its influence on the transport processes is not only limited to proton transport but it may also affect gas transport, electron conductivity and water management of the cell. However, experimental techniques to study the polymer electrolyte distribution are scarce. In this paper we present various approaches based on scanning electron microscopy (SEM) and transmission electron microscopy (TEM) to characterize the polymer electrolyte distribution. The methods presented include staining of the polymer electrolyte with heavy metal ions, energy dispersive X-ray (EDX) mapping and energy filtered imaging (EFI). Their use for the analysis of the polymer electrolyte distribution and electrode structure will be presented and current limitations of these techniques will be discussed. (C) 2007 Elsevier B.V. All rights reserved.