The nitrogenous nucleophile electrooxidation reaction (NOR) plays a vital role in the degradation and transformation of available nitrogen. Focusing on the NOR mediated by the β‐Ni(OH)2 electrode, we decipher the transformation mechanism of the nitrogenous nucleophile. For the two‐step NOR, proton‐coupled electron transfer (PCET) is the bridge between electrocatalytic dehydrogenation from β‐Ni(OH)2 to β‐Ni(OH)O, and the spontaneous nucleophile dehydrogenative oxidation reaction. This theory can give a good explanation for hydrazine and primary amine oxidation reactions, but is insufficient for the urea oxidation reaction (UOR). Through operando tracing of bond rupture and formation processes during the UOR, as well as theoretical calculations, we propose a possible UOR mechanism whereby intramolecular coupling of the N−N bond, accompanied by PCET, hydration and rearrangement processes, results in high performance and ca. 100 % N2 selectivity. These discoveries clarify the evolution of nitrogenous molecules during the NOR, and they elucidate fundamental aspects of electrocatalysis involving nitrogen‐containing species. During urea electrooxidation over a Ni(OH)2 electrode the dehydrogenation reaction from β‐Ni(OH)2 to β‐Ni(OH)O can lead to spontaneous urea dehydrogenation. Spontaneous intramolecular coupling of the N−N bond and hydration of urea dehydrogenation intermediates play important roles in the oxidation path from urea to N2 and CO2.