Microbial fuel cells (MFCs) have emerged as a promising alternative technology for sustainable energy production, as they generate electricity while simultaneously treating wastewater through the metabolic activities of microorganisms. This study designed, assembled, and evaluated a constructed wetland–microbial fuel cell (CW-MFC) system for the dual purpose of river water treatment and bioelectricity generation. The system utilized actual river water as the wastewater source and incorporated Megathyrsus maximus, an invasive aquatic weed, as the wetland vegetation. Performance evaluation was conducted by monitoring voltage generation throughout the operational period, constructing polarization curves, and calculating key electrochemical parameters, including power output and power density. In addition, water quality improvement was assessed by analyzing chemical oxygen demand (COD), nitrate concentration, and phosphate concentration before and after treatment. Results showed that the CW-MFC system generated an average voltage of 50.50 mV, an average power output of 5.10 μW, and an average power density of 1.62 mW/m². Significant improvements in water quality were also observed, particularly in the reduction of nitrate levels and COD, indicating effective pollutant removal. The findings demonstrate that CW-MFC technology integrated with Megathyrsus maximus offers a viable and environmentally sustainable approach for renewable energy generation and river water remediation. This system presents a cost-effective and eco-friendly alternative for addressing both energy and water quality challenges.