Boron cluster chemistry roared to life in the 20th century with seminal discoveries outlining the incredibly versatile chemistry of boron, producing a range of neutral and ionic boron compounds that paved the way for a robust suite of hybrid materials that incorporate these electronically delocalized inorganic clusters with the additional organic flexibility. Looking toward further materials research in the 21st century, these stable, inorganic polyhedral borane clusters discovered during previous century will provide a particularly fertile ground for exploration. These stable clusters have already seen significant exploration, but their utility has been obscured by classical synthetic routes using highly toxic neutral borane compounds. This incongruity is quite ironic given the current variety of medical explorations conducted with the essentially nontoxic dodecahedral borane dianion. This article will lay out some essential context and outline key synthetic studies that may dramatically simplify access to these unique compounds to a broader community of materials scientists and engineers.