In all, this work shows how pulsed electrolysis is a powerful tool in promoting electrocatalytic coupling reactions. In particular, the partial oxidation of NH3 leads to a higher concentration of NHx species on the catalyst surface and thereby facilitates their coupling to CO2R intermediates in a new reaction mechanism and consequently greater efficiencies for C-N product generation. While CO2 and NH3 coupling was the model reaction in this study, we have shown that there are many avenues to explore in the use of downstream CO2R products, additional N-species and even C-S coupling. Finally, there is much room to explore in terms of catalyst design. Though this work used commercial Cu particles, the use of Cu with well defined facets or Cu-based alloys may be an effective strategy for precisely modulating the binding energy of key reactants and steering the reaction down a select pathway. In addition, the addition of secondary binding sites that, for example, bind N-species may stand to boost performance. In the end, with this newfound oxyreductive coupling strategy, the electrochemical construction of a wide gamut of important chemicals from simple building blocks is closer to practicality.