Photosystem I (PSI), in particular, is ideal for use in solar cells due to its innate ability to photoexcite electrons with a quantum efficiency approaching unity. In vivo, these electrons are then mediated to the water-soluble redox protein called ferrodoxin; in artificial biohybrid devices, these electron acceptor proteins must be replaced with electrodes and electrochemical mediators. In this work, novel PSI-based solar cells were prepared by using polyviologens as the electron-transport layer between the PSI protein and the indium tin oxide (ITO) anode. Redox polymer-modified electrodes are increasingly used as electron-transfer catalysts in electrochemical applications. Polyviologens are a unique class of organic polycationic polymers, which can rapidly accept excited state electrons from a primary donor such as PSI and subsequently donate them to a secondary acceptor. Our device is a unique example of the direct use of extracted PSI protein to create photoactive biohybrid electrodes and represents one of few reported methods for incorporating PSI into a solid-state device, eliminating the problems associated with wet photoelectrochemical cells, such as corrosion and leaks.