Biochar with highly porous structures and organic functional moieties can act as an efficient micro-substrate for bacterial interaction. This study explores the potential of biochar combined with a CoFe2O4 catalyst as an anode material in Microbial Fuel Cells (MFCs). To prevent bacterial clogging of the biochar pores, we strategically synthesized rod-shaped CoFe2O4 nano substrates. When decorated on the biochar surface, these nanorods served as pillars for bacterial growth, preventing pore clogging and enhancing the electron transfer mechanism. SEM and TEM images confirmed the presence of nanorods on the biochar surface. S. putrefaciens utilizes Co+2 and Fe+2 ions released from CoFe2O4 as electron acceptors, promoting their growth and colonization on the anode surface. The contact angle measurements of the fabricated anode showed it to be hydrophilic, with a water contact angle (θw) of 37.4°. OSP analyses revealed that the anode has a textured surface, further favoring bacterial adhesion and biofilm formation. The double-chambered MFC exhibited the highest current density of 32.225 A/m3. This study underscores the importance of biochar and the strategic enhancement of electrode performance through the surface tuning of nanocatalysts for application in microbial fuel cells.