In a phototroph-based microbial fuel cell (MFC), the photosynthetic conversion efficiencies of bacteria and algae are utilized to generate power with simultaneously achieving wastewater treatment. In addition, this technology has huge potential for addressing issues related to climate change and energy crisis by assisting in carbon capture and biodiesel production, respectively. The phototrophs capable of ejecting extracellular electrons can be employed in the anodic chamber and those capable of liberating oxygen can be employed in the cathodic chamber of MFC. Depending upon the contribution of phototrophs, the technology is known by different terminologies, namely photosynthetic microbial fuel cell (PMFC), biophotovoltaic (BPV) cell, and microbial carbon-capture cell (MCC). This chapter elaborates these techniques by laying a focus on the fundamentals of the technology along with the role of various abiotic and biotic factors in determining the overall performance of the cell. Furthermore, the possible applications and resource recovery potentials of these technologies have been discussed along with an examination of their bottlenecks and future perspective.