Biochar-assisted anaerobic digestion (AD) remains constrained due to the inefficient decomposition of complex organics, even with the direct interspecies electron transfer (DIET) pathway. The coupling of electrochemistry with the anaerobic biological treatment could shorten lengthy retention time in co-digestion by improving electron transfer rates and inducing functional microbial acclimation. Thus, this work investigated the potential of improving the performance of AD by coupling low-magnitude electric fields with biochar derived from the anaerobically digested biogas residue. Different voltages (0.3, 0.6, and 0.9 V) were applied at various stages to assess the impact on biochar-assisted AD. The results indicate that an external voltage of 0.3 V, coupled with 5 g/L of biochar, elevates CH yield by 45.5% compared to biogas residue biochar alone, and the coupled approach increased biogas production by up to 143% within 10 days. This finding may be partly explained by the enhanced utilization of substrates and the increased amounts of specific methanogens such as and . The abundance of the former increased from 4.0 to 11.3%, which enhances the DIET between microorganisms. Furthermore, the coupling method shows better potential for enhancing AD compared to preparing iron-based biochar, and these results present potential avenues for its broader applications.