Ampere‐Level Electrosynthesis of CO via Well‐Defined Pyridinic‐N Incorporated Cobalt Phthalocyanine

High‐rate CO electrosynthesis from CO 2 is vital for efficient CO 2 ‐CO‐C 2+ tandem conversion. Cobalt phthalocyanine (CoPc), featuring a Co‐N 4 site naturally favorable for CO production, suffers from low conductivity. Herein, a molecular engineering strategy is reported to construct cobalt tetra‐aza‐phthalocyanine (CoTAP) by incorporating four pyridinic‐N atoms at the β‐positions of the CoPc macrocyclic backbone, effectively enhancing both conductivity and intrinsic activity. The resulting CoTAP electrode achieves ≈100% CO selectivity at an ultralow onset overpotential of 140 mV (−0.25 V vs. RHE), significantly outperforming pristine CoPc (−0.57 V vs. RHE). Furthermore, it also delivers a record‐high CO current density of −1084 mA cm −2 , an exceptional mass activity of 24,636.4 A g −1 , and an ultrahigh turnover frequency of 73.4 s −1 , with excellent stability for 112 h at −150 mA cm −2 , surpassing all reported Pc‐based catalysts. Systematic analysis shows that pyridinic‐N incorporation alters the electronic environment around Co centers and reduces resistance to only 3.8% of CoPc. Theoretical calculations further confirm more favorable adsorption energies for key intermediates ( * COOH and * CO), underpinning the enhanced intrinsic activity. Collectively, these advancements maximize site‐specific reaction kinetics in CoTAP. This work presents a molecular‐level strategy to simultaneously boost conductivity and intrinsic activity for advanced CO 2 electroreduction.