Low efficiency of charge extraction (and conversely charge injection) across biotic–abiotic interfaces constitutes an obstacle to the integration of biological and electronic systems in high-performance bioelectronic devices. Advances in the promotion of charge transport across these typically nonconductive interfaces will have far-reaching implications in important applications such as alternative energy generation, bioelectrosynthesis, diagnostics, and environmental monitoring. This review highlights the use of synthetic materials to improve electrical interfacing between biological systems and electrodes, focusing specifically on whole cell bioelectrochemical systems. By taking advantage of a rich variety of materials chemistry and synthetic methodologies, significant improvements to the facilitation of charge transport across abiotic–biotic interfaces have been realized. The modifications of the bioelectronic interfaces presented herein include the use of organic small molecules, semiconducting and redox active polymers, inorganic nanoparticles, carbon nanotubes, graphene, hybrid organic–inorganic systems, and micro-/nanoelectrodes. However, design rules to guide material selection and choices regarding device architecture remain ambiguous. Establishment of a clearer understanding of bioelectronic charge transfer phenomena, their constituent pathways, and means of stimulating or selecting for different pathways is still work in progress. As such, great opportunities exist for materials scientists to contribute to these topics through design and implementation.