So far, most efforts in the design of electrosynthetic systems, including those for C-N bond formation, have focused on either applying a constant reductive or oxidative potential, where the electrode polarity remains unchanged and electrons flow unidirectionally. The crossover of oxidation or reduction products to the opposite electrode here is typically undesired. Although counterintuitive, we propose that the simultaneous coexistence of oxidative and reductive intermediates on a single catalyst would be an effective route promote heteroatom coupling electrosynthesis via a pulsed electrolysis.