The Energy System lab at the University of Trieste has carried out a study to investigate the reduction in performance of high temperature polymer electrolyte membrane (HTPEM) fuel cell membrane electrode assemblies (MEAs) when subjected to different ageing tests. In this study, start and stop cycles, load cycles, open circuit voltage (OCV) permanence and constant load profile were considered. Polarization curves (PC) together with electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) data were recorded during the ageing tests to assess the fuel cell performance. In this paper, experimental data are presented to confirm the test methodology previously proposed by the authors and to quantitatively correlate the performance degradation to the operational profiles. It was demonstrated that OCV condition, start and stop and load cycling increase degradation of the MEAs with respect to constant load operation. As expected, the OCV is the operational condition that influences performance degradation the most. Finally, the MEAs were analyzed with synchrotron small angle X-ray scattering (SAXS) technique at the Austrian SAXS beamline at Elettra-Sincrotrone Trieste to analyze the nano-morphological catalyst evolution. As for the catalyst morphology evolution, the ex situ SAXS methodology proposed by the authors is confirmed in its ability to assess the catalyst nanoparticles aggregation.