Fe-based catalysts for the oxygen reduction reaction at the cathode of polymer electrolyte membrane (PEM) fuel cells have been prepared using several highly microporous (defined as pores having a size <2 nm) carbon supports. The aim is to produce better performing catalysts as it is known that catalytic sites are hosted in the micropores of the carbon supports. All catalysts were loaded with a nominal Fe content of 0.2 wt% and were obtained by heat-treatment at 950 °C in pure NH3 atmosphere. It is demonstrated, however, that the use of highly microporous carbon supports does not lead to improved catalytic activity, as originally expected, since the surface of these micropores is devoid of the nitrogen functionalities necessary to build the catalytic sites. Also, it is shown that for these microporous carbon supports, it is only the new micropores, i.e. those created during NH3 etching at high temperature, that are capable of hosting catalytic sites.