The carbons incorporating FeNx electrocatalysts (FeTEPA/C-x) were fabricated via a facile chemical process. The nitrogen-rich species (tetraethylenepentamine) were complexed with iron precursors (FeCl3) on carbon blacks (Vulcan XC-72) and treated under high temperature in a nitrogen atmosphere. These resultant catalysts were characterized by a variety of different spectroscopic and analytical techniques such as X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) measurements. Experimentally, the electrocatalytic performance of oxygen reduction for FeTEPA/C-2.7, which was found to have an approximate four electron transfer, was observed to be surpassing among all FeTEPA/C-x electrocatalysts. This may be attributed to its unique properties, including the higher nitrogen content, more pyridinic-N sites and probable formation of Fe–N–C active centers which were evidenced by XAS.