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• Reaction mechanism of the aminopyridine compound was studied by DFT calculations. • The thermodynamic energy barriers and hydrogen transfer manners were identified. • Aminopyridine derivatives were designed and the catalytic activity was studied. • Advantageous effects of electrochemical catalytic CO 2 reduction were clarified. We report here the electrochemical reaction mechanism of CO 2 reduction catalyzed by aminopyridine cobalt complex. The thermodynamic energy barriers and the rate-determining step are unveiled on the basis of DFT calculation results. In addition, a computational investigation for the purpose of predicting the catalytic reactivity of a series of aminopyridine metal (Mn, Ni, Cr) complexes has also been carried out. The compound with Cr as central metal exhibits a low energy barrier in the rate-determining step. On the other hand, the electron-donating substituents are revealed to be able to reduce the energy barrier of the rate-determining step by increasing the eletrophilicity of the oxygen atom in C-OH moiety. Furthermore, the compounds with π-π conjugation in meso -positions cannot adsorb the CO 2 molecule and therefore do not show catalytic activity for CO 2 reduction. In contrast, the compounds with p-π conjugation in meso -positions exhibit a good catalytic activity for the reduction of CO 2. [ABSTRACT FROM AUTHOR]