In pursuit of advancing the electrooxidation of amines, which is typically encumbered by the inertness of C(sp3)-H/N(sp3)-H bonds, our study introduces a high-performance electrocatalyst that significantly enhances the production efficiency of vital chemicals and fuels. We propose a novel electrocatalytic strategy employing a uniquely designed (NixCo1-x)Se2-R electrocatalyst, which is activated through Se-O exchange and electron orbital spin manipulation. This catalyst efficiently generates M4+ species, thus enabling the activation of lattice oxygen and streamlining the electrooxidation of amines. Empirical evidence from isotope labeling, molecular probes, and computational analyses indicates that the electrocatalyst fosters the formation of energetically favorable peroxy radical intermediates, which substantially expedite the reaction kinetics. The refined electrocatalyst achieves an exceptional current density of 20 mA cm-2 at a potential of 1.315 V, with selectivity surpassing 99% for propionitrile, while demonstrating remarkable stability over 560 h. This work emphasizes the criticality of deciphering the fundamental mechanisms of amine electrooxidation and charts a more sustainable pathway for the nitrile and hydrogen production, marking a substantial advancement in the field of electrocatalysis.