Microbial fuel cells and biophotovoltaics represent promising technologies for green bioelectricity generation. However, these devices suffer from low durability and efficiency that stem from their reliance on living organisms to act as catalysts. Such limitations can be overcome with augmented capabilities enabled by nanotechnology. This review presents an overview of the different nanomaterials used to enhance bioelectricity generation through improved light harvesting, extracellular electron transfer, and anode performance. The implementation of nanomaterials in whole-cell energy devices holds promise in developing bioelectrical devices that are suitable for industry.