Vanadaborane, [(CPV)(2)(B2H6)(2)] (CP = eta(5)-C5H5), 1 reacts with elemental sulfur to afford the hexasulfide cluster [(CPV)(2)S-4(mu-eta(1)-S-2)], 2 in high yield. Compound 2 is a notable example of an organovanadium sulfide cluster in which the [V2S4] atoms define a bicapped tetrahedron framework, with one mu-eta(1)-S-2 ligand bridged the two (CpV) moieties. The sulfur atom in [V2S4] core in 2 is a four-skeletal-electron donor isoelectronic with the BH3 unit; therefore, the replacement of boron hydride in I by four sulfur atoms necessitates the formation of a bicapped tetrahedron [V2S4] framework. Furthermore, this is the only reported example of a bimetallic hexasulfide cluster containing vanadium. Pyrolysis of 1 with bis-chalcogenide ligands such as Ph2S2 and Bz(2)Se(2) (Bz = PhCH2), results in the formation of substituted vanadahexaboranes [(CPV)(2)B4H12-xLx], 3-5 (3: L = SPh: x = 3; 4: L = SPh, x = 2; 5: L = SeBz: x = 1) in modest yield. All these new compounds have been characterized by mass, H-1, B-11, C-13 NMR spectroscopy, and elemental analysis, and the structural types were unequivocally established by crystallographic analysis of compounds 2-5.