This chapter presents the current state of research on bioelectrochemical systems that include phototrophic organisms. First, we describe what is known of how phototrophs transfer electrons from internal metabolism to external substrates. This includes efforts to understand both the source of electrons and transfer pathways within cells. Second, we consider technological progress toward producing bio-photovoltaic devices with phototrophs. Efforts to improve these devices by changing the species included, the electrode surfaces, and chemical mediators are described. Finally, we consider future directions for this research field.