The field of organic electronics continues to be driven by new charge-transporting materials that are typically processed from toxic organic solvents incompatible with biological environments. Over the past few decades, powerful examples of electrical transport as mediated through protein-based macromolecules have fueled the emerging area of organic bioelectronics. These attractive bioinspired architectures have enabled several important applications that draw on their functional electrical properties, ranging from field-effect transistors to piezoelectrics. In addition to naturally occurring protein biomacromolecules, unnatural oligopeptide self-assemblies and peptide-π conjugates also exhibit interesting electrical applications. This review provides an overview of electrical transport and electrical polarization in specialized biomaterials as manifested in solid-state device architectures.