A reinvestigation of the synthesis of [H5-nRh13(CO)(24)](n-) (n = 2, 3) led to isolation of a series of Rh-19, Rh-26, and Rh-33 high-nuclearity carbonyl and carbonyl-substituted rhodium clusters. The [Rh-19(CO)(31)](5-) (1) is electronically equivalent with [Pt-19(CO)(22)](4-), but poor crystal diffraction data of all salts obtained to date have prevented its geometrical analysis. The structures of Rh-26(CO)(29)(CH3CN)(11) (2) as 2 center dot 2CH(3)CN and [Rh-33(CO)(47)](5-) (3) as [NEt4](5)[3]center dot Me2CO were determined from complete X-ray diffraction determinations. The latter two species adopt polyicosahedral metal frameworks, and notably, [Rh-33(CO)(47)](5-) represents the molecular group 9 metal carbonyl cluster of highest nuclearity so far reported.