Relying on surface functional groups and graphitized structure, pyrogenic carbon (PC) was reported to facilitate microbial extracellular electron transfer (EET), which plays a crucial role in diverse biogeochemical reactions. However, little is known about the role of electrical capacitance on EET between microbes and PCs. Here, PCs were obtained from fermented steam bread after carbonization at different temperatures from 700 °C to 1100 °C. PC-900 exhibited the lowest charge transfer resistance and highest electrical capacitance, ascribed to combined effects of graphitic structure and hierarchical porous structure. The interfacial EET was further investigated by enriching electroactive biofilms on PC surface. Faster interfacial EET was demonstrated in PC-900. Maximum power density was proportional to electrical capacitance rather than conductivity. PC-900 enriched the most Geobacter sp., which was positively correlated with electrical capacitance according to the distance-based redundancy analysis. Electrical capacitance was suggested to act as electron pool to facilitate interfacial EET efficiency.