The commercial success of the electrochemical energy conversion technologies required for the decarbonization of the energy sector requires the replacement of the noble metal‐based electrocatalysts currently used in (co‐)electrolyzers and fuel cells with inexpensive, platinum‐group metal‐free analogs. Among these, Fe/N/C‐type catalysts display promising performances for the reduction of O₂ or CO₂ , but their insufficient activity and stability jeopardize their implementation in such devices. To circumvent these issues, a better understanding of the local geometric and electronic structure of their catalytic active sites under reaction conditions is needed. Herein we shed light on the electronic structure of the molecular sites in two Fe/N/C‐catalysts by probing their average spin state with X‐ray emission spectroscopy (XES). Chiefly, our in situ XES measurements reveal for the first time the existence of reversible, potential‐induced spin state changes in these materials.