The premise of most studies on the homogeneous electrocatalytic CO₂ reduction reaction (CO₂RR) is a good understanding of the reaction mechanisms. Yet, analyzing the reaction intermediates formed at the working electrode is challenging and not always attainable. Here, we present a new, general approach to studying the reaction intermediates applied for CO₂RR catalyzed by a series of cobalt complexes. The cobalt complexes were based on the TPA-ligands (TPA = tris(2-pyridylmethyl)amine) modified by amino groups in the secondary coordination sphere. By combining the electrochemical experiments, electrochemistry-coupled electrospray ionization mass spectrometry, with density functional theory (DFT) calculations, we identify and spectroscopically characterize the key reaction intermediates in the CO₂RR and the competing hydrogen-evolution reaction (HER). Additionally, the experiments revealed the rarely reported in situ changes in the secondary coordination sphere of the cobalt complexes by the CO₂-initiated transformation of the amino substituents to carbamates. This launched an even faster alternative HER pathway. The interplay of three catalytic cycles, as derived from the experiments and supported by the DFT calculations, explains the trends that cobalt complexes exhibit during the CO₂RR and HER. Additionally, this study demonstrates the need for a molecular perspective in the electrocatalytic activation of small molecules efficiently obtained by the EC-ESI-MS technique.