Sawdust-based biochar prepared (SDBC) at three pyrolytic temperatures were compared as additives to mesophilic anaerobic digestion (AD). SDBC prepared at 500 °C performed better in enhancing CH4 production than other SDBCs. Analyzing the crucial electro-chemical characteristics of the SDBCs revealed that the excellent electron transfer capacity of SDBC was significant to stimulate methanogenesis promotion. A long-term semi-continuous operation further confirmed that adding SDBC to AD system increased the maximum organic loading rate (OLR) from 6.8 g VS/L/d to 16.2 g VS/L/d, which attributed to the extremely low volatile fatty acids (VFA) accumulation. Microbial community succession analysis found that SDBC addition altered both bacterial and archaea structure greatly. More importantly, the syntrophic and electro-active partners of Petrimonas and Methanosarcina synergistically enriched under high OLR condition were responsible for the high-efficient VFA degradation, which suggested that SDBC likely acted as redox-active mediator to facilitate direct interspecies electron transfer between the syntrophic partners for high-efficient syntrophic methanogenesis process.