AbstractCO₂ electroreduction could be improved by applying conceptualized strategies to overcome catalytic bottlenecks. In this regard, we report two new cobalt(II) complexes [Co(Py₂^RN₃)(OTf)](OTf) (Co^R, R=H, Me) based on a new C₂‐symmetric pentacoordinate chiral ligand that are active on the electrochemical CO₂ reduction to CO. One of the complexes has a N−H group oriented towards the CO₂ binding site (Co^H), while the other has a N−Me group with the same orientation (Co^Me), as showed by X‐ray diffraction. We have studied the effect of introducing hydrogen bonding sites, i. e. N−H in Co^H, as a strategy to stabilize reaction intermediates. The complex bearing coordinating unprotected N−H group (Co^H) displays catalytic CO₂ reduction at the Co^II/I redox potential (−1.9 V vs. Fc, ca. 40 % FY_CO) whereas Co^Me shows CO₂ reduction at the Co^I/0 redox pair. FTIR‐SEC and DFT calculations identified a [Co^I−CO]⁺ cation as catalytic intermediate. The beneficial effect of the N−H group has been attributed to the stabilization of reaction intermediates or transition states and by the larger electron‐donating capacity, thus enhancing the nucleophilic character of the Co^I intermediate. The study also points to the CO dissociation from the Co(I)−CO resting state intermediate as one of the bottlenecks of the catalytic cycle, which can be overcome with light irradiation, resulting in an increase of the total CO production (−1.9 V, 81 % FY_CO, 11.2 TON_CO) at the Co^II/I redox potential.