A thick and electroactive biofilm is the key to the successful development of microbial electrochemical systems and technologies (METs). In this study, intact anaerobic granular sludge (AGS), which is a spherical and dense microbial association, was successfully demonstrated as a novel and efficient biocatalyst in METs such as microbial fuel cells. Three different strategies were explored to shift the microbial composition of AGS from methanogenic to exoelectrogenic microbes, including varying the external resistance and organic loading and manipulating the anode potential. Among all the strategies, only with positive anode potential, AGS was successfully shifted from methanogenic to exoelectrogenic conditions, as indicated by the significantly high current response (10.32 A/m2) and 100% removal of organic carbon from wastewater. Moreover, the AGS bioanode showed no significant decrease in current generation and organic removal at pH 5, indicating good tolerance of AGS to acidic conditions. Finally, 16S rRNA sequencing revealed the enrichment of exoelectrogens and inhibition of methanogens in the microbial community of AGS after anode potential control. This study provides a proof of concept for extracting electrical energy from organic wastes by exoelectrogenic AGS along with simultaneous wastewater treatment and meanwhile opens up a new paradigm to create an efficient and cost-effective exoelectrogenic biocatalyst for boosting the industrial application of METs.