An electric potential (EP) was applied to enhance biotreatment of anaerobically-treated leachate from municipal solid waste incineration plants using a partial nitritation-Anammox system. At an optimal EP difference of 0.06 V, total nitrogen removal efficiency reached 71.9%, 17.3% higher than the control system without an EP. Removal of organic matter was also stimulated with the EP, particularly macromolecules with molecular weight >20 kDa in the leachate. Applying EP also promoted production of extracellular polymeric substances and improved the protein/polysaccharide ratio. High-throughput DNA sequencing revealed that Anammox bacteria in the genus Candidatus Kuenenia were enriched for on electrodes with the applied EP. Heterotrophic denitrifiers, which potentially could degrade organic macromolecules, were also more abundant on the electrodes with EP compared with the control reactor. These results show that applying an EP could be a useful strategy in Anammox technologies treating real wastewater high in ammonia and refractory organic compounds.