Algae are living organisms with significant applications in material science. They are mostly organic carbon structures, which makes them a good choice for fabricating carbon-based electrodes. Researchers have studied Microbial Fuel Cell (MFC) technology for a decade, considering it an efficient energy generation technique. To improve the ability of MFCs to generate electricity, electrode materials that are both affordable and extremely effective must be developed. MFCs with algal electrodes serve as renewable, cost-effective, innovative, and sustainable power production systems. This chapter discusses the various configurations of photosynthetic MFC, as well as the integration of microalgae at the anode and cathode of MFC. The chapter also explains the mechanism of extracellular electron transfer at the anode and the process of carbon dioxide sequestration through photosynthesis at the cathode. The chapter delves into the role of algae in different configurations of MFCs, as well as various factors affecting their performance in terms of power generation. Insights into the advantages and limitations of bioanode and biocathode have been provided. The chapter concludes by proposing a greener desalination approach by integrating algae into microbial desalination cells.