The light reactions of natural photosynthesis can be manipulated towards electricity generation in photo-bioelectrochemical cell (PBEC) as demonstrated in our earlier work. The photosynthetic reactions occur in the thylakoid membrane and involve a complex set of redox reactions that result in the transfer of electrons between protein complexes. The electrons from the photosynthetic reactions can be channeled towards an external electrode for electricity generation by inhibiting the photosynthetic protein complexes in order to divert the flow of electrons towards to desired electron transport path within the photosynthetic membrane. Investigation using site-specific photosynthesis inhibitors revealed that the electrons generated through water oxidation reaction from photosystem II complex can be diverted to the external electrode for photocurrent generation primarily through the plastoquinone pool. Besides site specific inhibition, other approaches to increase photocurrent generation were investigated. One of those approaches is to engineer photosynthetic organisms such as Synechococcus elongatus PCC7942 with an outer membrane cytochrome (OmcS) derived from dissimilatory metal reducing bacteria which increase the photocurrent generation at an external electrode by two fold. This paper will summarize some of our recent work on multiple different approaches to enhance photocurrent generation through an understanding of electron transport reactions in photosynthetic membranes.