Electrochemical conversion of CO2 into valued products is one of the most important issues but remains a great challenge in chemistry. Herein, we report a novel synthetic approach involving prolonged thermal pyrolysis of hemin and melamine molecules on graphene for the fabrication of a robust and efficient single‐iron‐atom electrocatalyst for electrochemical CO2 reduction. The single‐atom catalyst exhibits high Faradaic efficiency (ca. 97.0 %) for CO production at a low overpotential of 0.35 V, outperforming all Fe‐N‐C‐based catalysts. The remarkable performance for CO2‐to‐CO conversion can be attributed to the presence of highly efficient singly dispersed FeN5 active sites supported on N‐doped graphene with an additional axial ligand coordinated to FeN4. DFT calculations revealed that the axial pyrrolic nitrogen ligand of the FeN5 site further depletes the electron density of Fe 3d orbitals and thus reduces the Fe–CO π back‐donation, thus enabling the rapid desorption of CO and high selectivity for CO production. High five! Prolonged thermal pyrolysis of hemin (H) and melamine (M) on graphene (G) provided a robust single‐iron‐atom electrocatalyst for CO2 reduction. The single‐atom catalyst exhibited high Faradaic efficiency (ca. 97 %) for CO production at low overpotential (0.35 V) owing to the presence of highly efficient dispersed FeN5 active sites supported on N‐doped graphene through an additional axial ligand coordinated to FeN4 (see picture; Fe red, N blue).