Microbial fuel cells (MFCs) provide a new opportunity to produce sustainable energy from the treatment of the organic matter in wastewater. However, the power density of MFCs for large‐scale application is limited by the performance of anode, with one of the major factors being low bacterial adhesion capacity. In this work, a novel macroporous sugarcane carbon (SC) is prepared by a direct carbonization process, and is used as anode material in a packed MFC. A maximum power density of 59.94±2.81 W m−3 is achieved in an MFC equipped with the SC anode, which is 2.62 times higher than that of the granular activated carbon (GAC) anode. A microbial analysis shows that the SC anode has a higher amount of biomass and the abundance of Geobacter is 6.6 times higher than that of the GAC anode, which indicates that the SC anode has higher biocompatibility. Further studies show that the macroporous structure, high surface roughness, large surface hydrophobicity and low absolute value of zeta potential favor bacterial adhesion to the SC anode surface. Therefore, this study provides an excellent anode material for high‐performance MFCs, and reveals the impact of physicochemical properties on power generation.