Constructed wetland-coupled microbial fuel cell systems (CW-MFCs) incorporate an aerobic zone and an anaerobic zone to generate electricity that achieves the oxidative degradation of contaminants. However, there are few reports on the performance of such coupled systems. In this study, we determined the optimal configuration of CW-MFCs to characterize their electricity generation performance. Based on the results using different levels of dissolved oxygen among the CW-MFCs, we concluded that a 20-cm distance between the anode and cathode produced an optimal removal of chemical oxygen demand (COD) of 94.90% with a 0.15 W/m 3 power density, 339.80 Ω internal resistance, and 0.31% coulombic efficiency. In addition, a COD of 200 mg/L provided greater electricity generation (741 mV open circuit voltage, 0.20 W/m 3 power density, 339.80 Ω internal resistance, and 0.49 mA current) and purification ability (90.45% COD removal) to meet system COD loading limitations than did higher COD values. By adding 50 mM phosphate buffer solution to synthetic wastewater, relatively high conductivity and buffer capacity were achieved, resulting in improvement in electricity generation. These findings highlight important aspects of bioelectricity generation in CW-MFCs.