To illustrate the indispensable role of electrolysis for the reaction outcome, we conducted experiments under pure O2 as terminal oxidant (Figure ). The yields were significantly reduced to less than 40%. To identify the cathodic half-reaction, we systematically analyzed the headspace of the reaction vessel using headspace gas chromatography. The oxygen reduction reaction (ORR) was comprehended as a possible cathodic reaction in the transformation (see Figure in the Supporting Information) and the oxygen consumption was faster in the presence of electricity (See Supporting Information for details). Literature precedents on the electrochemical synthesis of azo compounds further supported our analysis. The oxygen consumption was further quantitatively measured, where significantly accelerated oxygen consumption and product formation were observed under mild electrochemical conditions (Faradaic efficiency = 22%) (Figure ). In this context, a meticulously planned combination of anodic oxidation with hydrogen evolution reaction (HER) bears a distinguished potential toward a green hydrogen economy. Thus, the reaction was performed under an inert atmosphere (see Supporting Information), where the cathodic reaction was switched to HER as the main pathway. Unlike the aerobic conditions, hydrogen gas formation was detected from the headspace of the reaction vessel during the transformation (Figure ). We also quantitatively determined the evolution of hydrogen gas (nH2/n5=0.43), demonstrating cobaltaelectro-catalysis as a sustainable technique for the merger with HER (Figure ). Additionally, the catalytic reaction was monitored via high-resolution mass-spectrometry (HRMS), where the formation of heteroleptic cobalt(II)-complex and cobalt(III)-complex were detected as crucial intermediates (see Supporting Information for details).