We report methods for the synthesis of vertex-differentiated icosahedral closo-boranes. A single B鈥揙H vertex of the icosahedral borane [closo-B12(OH)12]2鈥?/sup> was derivatized to prepare [closo-B12(OR)(OH)11]2鈥?/sup> using optimized alkylation conditions and purification procedures. Several representative vertex-differentiated icosahedral closo-boranes were prepared utilizing carbonate ester and azide鈥揳lkyne click chemistries on the surface of the closo-B122鈥?/sup> core.