Syntheses and structural characterization of supraicosahedral rhodaborane clusters are reported. Reaction of [(Cp*RhCl2)(2)], (Cp* = eta(5)-C5Me5) with [LiBH4 center dot thf] followed by thermolysis with excess of [BH3 center dot thf] afforded 16-vertex closo-[(CP*Rh)(3)B12H12Rh{CP*RhB4H9}], 1, 15-vertex [(CP*Rh)(2)B13H13], 2, 12-vertex [(Cp*Rh)(2)B10Hn(OH)(m)], (3a: n = 12, m = 0; 3b: n = 9, m = 1; 3c: n = 8, m = 2) and 10-vertex [(Cp*Rh)(3)B7H7], 4, and [(Cp*Rh)(4)B6H6], 5. Cluster 1 is the unprecedented 16 vertex cluster, consists of a sixteen vertex {Rh4B12} with an exo-polyhedral {RhB4} moiety. Cluster 2 the first example of a carbon free 15 vertex supraicosahedral metallaborane, exhibits icosihexahedron geometry (26 triangular faces) with three degree-six vertices. Clusters 3a-c have 12-vertex isocloso geometry, different from that of icosahedral one. Clusters 4 and 5 are attributed to the 10-vertex isocloso geometry based on 10-vertex bicapped square antiprism structure. In addition, quantum-chemical calculations with DFT methods at the BP86 level of theory have been used to provide further insight into the electronic structure and stability of the optimized structures which are in satisfactory agreement with the structure determinations All the compounds have been characterized by IR, H-1, B-11, C-13 NMR spectroscopy in solution, and the solid state structures were established by crystallographic analysis of compounds 1-5.