Metal, nitrogen‐doped carbon materials have attracted interest as heterogenous catalysts that contain MNx active sites that are analogous to molecular catalysts. Of particular interest is Ni,N‐doped carbon, a catalyst that is active for the electrochemical reduction of CO2 to CO. Critical to the understanding of these materials is proof of single atomic sites and characterization of the environment surrounding the metal atom; however, directly probing this coordination remains challenging. This challenge is addressed by combining scanning transmission electron microscopy (STEM), single atom electron energy loss spectroscopy (EELS), and time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS). Through STEM imaging, atomic dispersion of Ni in the carbon framework is confirmed and image analyses are utilized to give semiquantitative estimates of neighbor distance distributions and site densities of Ni atoms. Atomic resolution EELS demonstrates that N and Ni are colocated at the single Ni atom sites suggesting Ni–N coordination. ToF‐SIMS reveals a distribution of NiNxCy− fragments that reflect the Ni–N bonding environments within Ni,N‐doped carbon. The fragmentation from Ni,N‐doped carbon is similar to Ni phthalocyanine, suggesting the existence of heterogenized, molecular‐like NiN4 active sites which motivates future studies that leverage insight from molecular catalysis design to develop next‐generation heterogeneous catalysts.