This study investigates the electrocatalytic CO₂ reduction reaction (CO₂RR) using a series of cobalt complexes with tris(2-pyridylmethyl)amine (TPA) ligands modified by amino groups in the secondary coordination sphere. The authors developed an online coupling of an electrochemical cell with electrospray ionization mass spectrometry (EC-ESI-MS) to monitor the reaction intermediates. By combining electrochemical experiments, EC-ESI-MS, and density functional theory (DFT) calculations, they identified and characterized key reaction intermediates, including the CO₂RR and competing hydrogen evolution reaction (HER). The study revealed that the amino groups in the secondary coordination sphere undergo in situ transformation into carbamates upon CO₂ reduction, leading to an alternative HER pathway. This pathway is faster and more efficient than the conventional HER pathway. The interplay of three catalytic cycles, supported by DFT calculations, explains the observed trends in the CO₂RR and HER activities of the cobalt complexes. The study highlights the importance of a molecular perspective in understanding the electrocatalytic activation of small molecules.This study investigates the electrocatalytic CO₂ reduction reaction (CO₂RR) using a series of cobalt complexes with tris(2-pyridylmethyl)amine (TPA) ligands modified by amino groups in the secondary coordination sphere. The authors developed an online coupling of an electrochemical cell with electrospray ionization mass spectrometry (EC-ESI-MS) to monitor the reaction intermediates. By combining electrochemical experiments, EC-ESI-MS, and density functional theory (DFT) calculations, they identified and characterized key reaction intermediates, including the CO₂RR and competing hydrogen evolution reaction (HER). The study revealed that the amino groups in the secondary coordination sphere undergo in situ transformation into carbamates upon CO₂ reduction, leading to an alternative HER pathway. This pathway is faster and more efficient than the conventional HER pathway. The interplay of three catalytic cycles, supported by DFT calculations, explains the observed trends in the CO₂RR and HER activities of the cobalt complexes. The study highlights the importance of a molecular perspective in understanding the electrocatalytic activation of small molecules.