The construction of functional N-containing active biomolecules and bidentate nitrogen ligands by electroreductive pyridylation of N-heteroaromatics is an eye-catching task and challenge. A simple and practical electroreductive-induced C3 pyridylation of quinoxalin-2(1H)-ones with readily available cyanopyridines is reported. More than 36 examples are supplied, and the reaction performed in >95% yield. The present protocol provides a convenient, efficient, and gram-scale synthesis strategy for a series of new types of potential bidentate nitrogen ligands.