The Anammox anaerobic fluidized bed microbial fuel cell (Anammox AFB-MFC) exhibits exceptional performance in both nitrogen removal and electricity generation, effectively eliminating ammonia nitrogen (NH4+-N) and nitrite nitrogen (NO2−-N) pollutants. This technology offers the advantages of high efficiency in nitrogen removal and low electricity consumption. By coupling an AFB with an MFC, the Anammox AFB-MFC was developed through the introduction of anaerobic ammonia-oxidizing bacteria (AnAOB) into MFC. Anammox AFB-MFC’s nitrogen removal ability was found to be superior at an influent COD concentration of 200 mg/L, as determined by a study conducted under unchanged conditions. Subsequently, an open and closed-circuit experiment was performed on the Anammox AFB-MFC system while maintaining a COD concentration of 200 mg/L in the influent. Remarkably, the reactor exhibited significantly enhanced nitrogen removal performance when electricity generation occurred. Throughout the entire experimental process, the reactor consistently maintained high nitrogen removal efficiency and electricity production performance. Under optimal experimental conditions, the reactor achieved a remarkable nitrogen removal rate of 91.8% and an impressive output voltage of 439.1 mV. Additionally, the generation of Anammox bioparticles in MFC significantly contributed to efficient pollutant removal. This study elucidates the impact of organic matter on both the nitrogen removal and electricity generation capabilities of Anammox AFB-MFC, as well as highlights the synergistic effect between MFC electricity generation and nitrogen removal in the reactor.