A novel hybrid single chamber microbial fuel cell is described in which a TiO2 nanotube array (TNT) photoanode is coupled with a conventional bioanode to achieve simultaneous degradation of methylene blue (MB) dye with improved power generation. As compared to a conventional microbial fuel cell (MFC), the described hybrid-MFC exhibits enhanced power density (14%), current density (33%), and voltage (4%) while simultaneously degrading MB dye, 82.79% after 3.5 h of operation under simulated solar light illumination. The key factor attributed to the enhanced performance is the addition of photogenerated electrons to the MFC external circuit. The effect of various design configurations is also investigated, such as the presence of an air cathode, anode type, and illumination. The hybrid-MFC strategy provides new directions for productive and economical utilization of microbial fuel cells.