Magnetite (Fe3O4) is extensively applied to enhance efficacy of anaerobic biological treatment systems designed for refractory wastewater. However, the interaction between magnetite, organic pollutants and microorganisms in digestion solution is constrained by magnetic attraction. To overcome this limitation and prevent magnetite aggregation, the core-shell composite materials with carbon outer layer enveloping magnetite core particles (Fe3O4@C) were developed. The impact of Fe3O4@C with varying Fe3O4 mass ratios on the anaerobic methanogenesis capability in the treatment of chloramphenicol (CAP) wastewater was investigated. Experimental results demonstrated that Fe3O4@C not only enhanced chemical oxygen demand (COD) removal efficiency and biogas production by 2.42-13.18% and by 7.53%-23.25%, respectively, but also reduced the inhibition of microbial activity caused by toxic substances and the secretion of extracellular polymeric substances (EPS) by microorganisms responding to adverse environments. The reinforcing capability of Fe3O4@C increased with the rise in Fe3O4 content. Furthermore, High-throughput pyrosequencing illustrated that Fe3O4@C enhanced the relative abundance of Methanobacterium, a hydrogen-utilizing methanogen capable of participating in direct interspecies electron transfer (DIET), by 5%. Metagenomic analysis indicated that Fe3O4@C improved the decomposition of complex organics into simpler compounds by elevating functional genes encoding key enzymes associated with organic matter metabolism, acetogenesis, and hydrogenophilic methanogenesis pathways. These findings suggest that Fe3O4@C have the potential to strengthen both the hydrogenophilic methanogenesis and DIET processes. This insight offers a novel perspective on the anaerobic bioaugmentation of high-concentration refractory organic wastewater.