The incorporation of polyhedral boranes into novel photoluminescent materials is an area with increasing interest. While the neutral carboranes have been widely investigated for this purpose, the dodecaborate ion has received much less attention. Herein we report a significant expansion to the scope of substitution reactions for the dodecaborate ion, whereby this cluster was observed to react directly with a wide range of arenes in a step-wise and controlled manner. In the products of these reactions, the dodecaborate ion serves as a core upon which up to nine mono-or polycyclic aromatic hydrocarbon ligands are exohedrally bonded. Spectroscopic evidence suggests the presence of conjugation between the p systems of the aryl ligands and the dodecaborate core, resulting in materials which exhibit high solution-phase photoluminescence, as well as molar absorptivities and Stokes shifts that are significantly larger than those of the free arenes from which they were derived. We propose that this broad reactivity is a valuable synthetic tool for the incorporation of polyhedral boron into novel organic structures.