Batch experiments were conducted using biochar (BC) to promote stable and efficient methane production from thermophilic co-digestion of food waste (FW) and waste activated sludge (WAS) at feedstock/seed sludge (F/S) ratios of 0.25, 0.75, 1.5, 2.25, and 3. The results showed that the presence of BC dramatically shortened the lag time of methane production and increased the methane production rate with increased organic loading. The higher buffer capacity and large specific surface area of BC promoted microorganism growth and adaption to VFAs accumulation. Additionally, the electron exchange in syntrophic oxidation of butyrate and acetate as intermediate products was significantly facilitated by BC possibly due to the selective succession of bacteria and methanogens which may have participated in direct interspecies electron transfer, in contrast with the control group with low-efficient electron ferried between syntrophic oxidizers and methanogens using hydrogen as the electron carrier.