Toluene degradation and electricity generation were examined under varying toluene doses. Addition of pyocyanin was evaluated for effectiveness in improving electricity generation via toluene degradation, and the mechanisms of improved electricity generation were analyzed. Supplemental pyocyanin achieved a 3.64-fold increase in maximum power density from 4.69 to 21.76mW/m2 and a 13-fold increase in Coulombic efficiency (CE) from 0.83% to 11.62%. Addition of pyocyanin significantly improved electricity generation by reducing system impedance, increasing electron density and substantially lowering the internal resistance of MFC (from 500 to 100 Ω). The results of this investigation not only demonstrated the possibility of adding pyocyanin for enhanced power production in a toluene-fed MFC but also can be used as a basis for future assessments of the power generation capacity of MFCs that were used to treat xenobiotics-contaminated wastewater, such as toluene.