In this paper we report an investigation of the degradation of the Pt/C electrocatalyst of an anodic membrane-electrode assembly (MEA) after 1000 h of operation in a laboratory single-cell PEMFC, using synchrotron-based space-resolved photoelectron spectroscopy. This study is complemented by the analysis of a pristine MEA and reference materials, as well as by electrochemical measurements, SEM imaging and energy-dispersive X-ray fluorescence spectroscopy (EDX). Catalyst ageing correlates with a corrugation of morphology, as observed by SEM and scanning photoelectron microscopy (SPEM), corresponding to Pt nanoparticle agglomeration. Moreover - on the basis of high lateral resolution SPEM, X-ray photoelectron spectroscopy (XPS) and EDX analyses, - we found that, after operation. Pt is transported onto the fibres of the gas-diffusion layer (GDL). Space-resolved XPS shows a peak shift of the Pt 4f(7/2) level to higher and lower binding energies with respect to Pt(1 1 1) and pristine Pt black, respectively, corresponding to nanocrystallinity in the first case and agglomeration in the second one. No oxidised Pt was found in any location of the anodically used MEA. (C) 2010 Elsevier B.V. All rights reserved.