The excessive accumulation of nitrogen pollutants (mainly nitrate, nitrite, ammonia nitrogen, hydrazine, and urea) in water bodies seriously disrupts the natural nitrogen cycle and poses a significant threat to human life and health. Electrolysis is considered a promising method to degrade these nitrogenous pollutants in sewage, with the advantages of high efficiency, wide generality, easy operability, retrievability, and environmental friendliness. For particular energy devices, including metal-nitrate batteries, direct fuel cells, and hybrid water electrolyzers, the realization of energy valorization from sewage purification processes (e.g., valuable chemical generation, electricity output, and hydrogen production) becomes feasible. Despite the progress in the research on pollutant electrodegradation, the development of electrocatalysts with high activity, stability, and selectivity for pollutant removal, coupled with corresponding energy devices, remains a challenge. This review comprehensively provides advanced insights into the electrodegradation processes of nitrogenous pollutants and relevant energy valorization strategies, focusing on the reaction mechanisms, activity descriptors, electrocatalyst design, and actuated electrodes and operation parameters of tailored energy conversion devices. A feasibility analysis of electrodegradation on real wastewater samples from the perspective of pollutant concentration, pollutant accumulation, and electrolyte effects is provided. Challenges and prospects for the future development of electrodegradation systems are also discussed in detail to bridge the gap between experimental trials and commercial applications.