Extracellular electron transfer from the biofilm surface to the electrode is the key step for the microbial fuel cell (MFC). More recently, graphene has attracted tremendous attentions for bioelectrochemical applications due to its good biocompatibility, high electrical conductivity and large surface area. In the current work, we report a facile and green synthesis of graphene-modified carbon paper (CP) as an efficient MFC anode through plant-mediated bioreduction coupled with self-assembly. Three-dimensional CFP uniformly wrapped by curled and wrinkled biosynthesized graphene enables more surface area for microbe adhesion and mass diffusion. Significantly, nontoxic and biodegradable biomolecules extracted from Eucalyptus leaves act as reducing agent and adsorb on the graphene, rendering the graphene surface become hydrophilic and biocompatible. Furthermore, the obtained graphene exhibit excellent bioelectrochemical interactions with the microbes. Equipped with the biosynthesized graphene-modified anode, the E. coli-catalyzed MFC delivered an enhanced maximum power density of 1158 mW/m2, 70% higher than a pristine graphene-modified one. This development provides not only a versatile and scalable synthesis strategy for biocompatible graphene-modified devices, but also indicates that biomolecules facilitate the extracellular electron transfer in bioelectrochemical process.