Microbial fuel cell (MFC) technology holds significant promise for the production of clean energy and treatment of pollutants. Nevertheless, challenges such as low power generation efficiency and the high cost of electrode materials have impeded its widespread adoption. The porous microstructure of biochar and the exceptional photocatalytic properties of rutile endow it with promising catalytic potential. In this investigation, we synthesized a novel Rutile–Biochar (Rut-Bio) composite material using biochar as a carrier and natural rutile, and explored its effectiveness as a cathode catalyst to enhance the power generation efficiency of MFCs, as well as its application in remediating heavy metal pollution. Furthermore, the impact of visible light conditions on its performance enhancement was explored. The X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) analysis validated the successful fabrication of rutile composites loaded with biochar. The maximum current density and power density achieved by the MFCs were 153.9 mA/m2 and 10.44 mW/m2, respectively, representing a substantial increase of 113.5% and 225% compared to the control group. In addition, biochar-supported rutile MFCs showed excellent degradation performance of heavy metal pollutants under light conditions. Within 7 h, the Cr6+ degradation rate reached 95%. In contrast to the blank control group, the removal efficiency of pollutants exhibited increases of 630.8%. The cyclic degradation experiments also showcased the remarkable stability of the system over multiple cycles. This study successfully integrated natural rutile and biochar to fabricate highly efficient cathode photocatalyst composites, which not only enhanced the power generation performance of MFCs but also presented an environmentally sustainable and economically viable method for addressing heavy metal pollution.