Anaerobic digestion (AD) is a promising technology in waste treatment and energy recovery. However, it suffers from long retention time and low biogas yield. In this study, novel nitrogen-doped biochar supported magnetite (NBM) was synthesized and applied to enhance the AD of waste-activated sludge. Results showed that NBM increased cumulative methane production and SCOD removal efficiency by up to 1.75 times and 15% respectively at 5 g/L compared with the blank. NBM enhanced both hydrolysis and methanogenesis process during AD and the activities of α-glucosidase, protease, coenzyme F420 and electron transport system were increased by 19%, 163%, 104% and 160% respectively at 5 g/L NBM compared with the blank. NBM also facilitated the secretion of conductive protein in extracellular polymeric substances as well as the formation of conductive pili, leading to 3.18-7.59 times higher sludge electrical conductivity. Microbial community analysis revealed that bacteria Clostridia and archaea Methanosarcina and Methanosaeta were enriched by the addition of NBM, and direct interspecies electron transfer might be promoted between them. This study provides a practical reference for future material synthesis and its application.