Despite extensive efforts, the electrocatalytic reduction of water using homogeneous/heterogeneous Fe, Co, Ni, Cu, W, and Mo complexes remains challenging because of issues involving the development of efficient, recyclable, stable, and aqueous‐compatible catalysts. In this study, evolution of the de novo designed dinitrosyl iron complex DNIC‐PMDTA from a molecular catalyst into a solid‐state hydrogen evolution cathode, considering all the parameters to fulfill the electronic and structural requirements of each step of the catalytic cycle, is demonstrated. DNIC‐PMDTA reveals electrocatalytic reduction of water at neutral and basic media, whereas its deposit on electrode preserves exceptional longevity, 139 h. This discovery will initiate a systematic study on the assembly of Fe(NO)2 motif into current collector for mass production of H2, whereas the efficiency remains tailored by its molecular precursor (L)Fe(NO)2. From complex to cathode: Dinitrosyl iron complex‐deposited electrodes feature smaller Tafel slope than platinum electrodes in 1 M KCl, as well as exceptional longevity for electrocatalytic H2‐generation. This approach opens the door for adapting other molecular catalysts into solid‐state cathodes.