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Solar radiation led into the planet earth by photosynthesis is the main energy basis for survival. Photosynthesis is a physico-chemical process where photosynthetic organism transform solar energy into chemical energy with simultaneous use of bioenergetic processes (Georgianna and Mayfield 2012; Strik et al. 2011). Photosynthetic microbial fuel cells (PhFCs) are newly established tools that harvest sun energy to yield electricity and has gained major attentiveness in applied and academic research due to its sustainable and renewable nature (Chandra et al. 2012; Venkata Mohan et al. 2014). PhFCs use plants or phototrophic microorganisms to trap sun light and use photo-bioelectrochemical system to produce bioelectricity (El Mekawy et al. 2014). This technology symbolizes a multi-disciplinary method to search for renewable energy. It represents the convergence for the life-sciences, chemical and physical science (McCormick et al. 2015; Xiao and He 2014). Microbial fuel cells (MFCs) are mainly focused towards anodic reaction with dark fermentation as microbial metabolic function. Analogous to dark fermentation, photosynthetic fuel cells (PhFC) or biophotovoltaic system (BPV) will also be functioned using photo synthetic bacteria (PSB) or algae/cyanobacteria based on their photosynthetic mechanism (oxygenic or anoxygenic) (Chandra et al. 2012; Rosenbaum et al. 2010a). Oxygenic photosynthesis based autotrophic PhFCs include diverse categories of MFC containing both heterotrophs and autotrophs (Venkata Mohan et al. 2010a, b, 2011) (Fig. 19.1). The current chapter has made an attempt to convey the present photosynthetic mechanism for PhFC application in understanding on the innate potential of photosynthetic mechanism.