Anammox exerts a crucial role in nitrogenous effluents remediation; nevertheless, nitrogen removal efficiency thresholds triggered by additional nitrate production poses a critical obstacle for anammox performance. Herein, Fe-Mn functionalized biochar (FeMn#BC) was synthesized and incorporated into anammox consortia to elicit the exogenous organics-independent metabolic potential of denitrifying bacteria, which decreased nitrate accumulation and achieved up to 90.69 ± 0.48 % total nitrogen removal efficiency. Enzyme content analysis indicated that FeMn#BC bolstered biometabolic vigour and electron transport system activity by stimulating the synthesis of heme c and NADH. Microbial community succession results demonstrated that FeMn#BC facilitated the proliferation of anammox bacteria (AnAOB) and nitrate-reducing functional bacteria. Metagenomic analysis uncovered that FeMn#BC increased the relative abundance of genes related to energy metabolism, nutrient-substrate ingestion, cofactor synthesis, and iron-manganese transport pathways. Candidatus Brocadia sp013360945 interacted nitrogen metabolism substrates and electrons with dominated denitrifying species PR03 sp. (dependent on endogenous organics and FeMn#BC-released Fe(II)), while interacted cofactors with other mutualistic bacteria possessing nitrate-reducing potential (e.g. ATM1 sp003577165). FeMn#BC-released Mn(II) served as an additional electron donor, augmenting electron availability for non-dominant anammox species like Candidatus Jettenia caeni and Candidatus. Kuenenia stuttgartiensis. This research highlights the critical mechanism of Fe-Mn synergism for overcoming the bottleneck of anammox nitrogen removal efficiency, and demonstrates the substantial potential of Fe-Mn functionalized materials to revolutionize the existing wastewater treatment technologies towards a carbon-free approach.