Transition metal (M)and nitrogen functionalized (Nx) carbonaceous (TM-Nx) electrocatalysts are emerging as possible alternatives to Platinum for fuel cell applications. As of now, X-ray Photoelectron Spectroscopy (XPS) is one of the key surface analysis techniques used for characterizing these heterogeneous nitrogen-functionalized electrocatalysts. However, it is challenging to derive detailed structure to property relationships from XPS alone. To overcome this limitation, computationally determined XPS binding energy shifts can help in the understanding of the types of self-assembled nitrogen and transition moieties present in these electrocatalysts. In the present study, DFT computations were used to assess the physiochemical and thermodynamic properties of graphitic-nitrogen and Fe-Nx moieties present in graphene and identified using DFT predicted core level shifts This synergy of experimental and computational results is imperative for the rational engineering and development of efficient non-PGM electrocatalysts.