The first structural characterization of the highly unsaturated nonacarbonyldivanadium V-2(CO)(9) is reported using density functional theory (DFT) with the B3LYP and BP86 functionals. A complicated collection of minima with rather closely spaced energies was found. However, none of these many V-2(CO)(9) isomers was found to have a sufficiently short vanadium-vanadium distance for the V-4-V quadruple bond required to give both metal atoms the favored 18-electron configuration. Triplet structures for V-2(CO)(9) were found to be competitive in energy with related singlet structures. Thus, the two lowest-energy isomers of V-2(CO)(9) are triplets. The four lowest-energy isomers of V-2(CO)g all have three very unsymmetrical bridging CO groups (typically "short" and "long" M-CO distances differing by 0.4-0.5 angstrom) rather than the symmetrical bridging CO groups found experimentally in Fe-2(CO)(9) and predicted for M-2(CO)(9) (M = Cr and Mn) from earlier studies. The V equivalent to V distances in each of these four isomers suggest a metal-metal triple bond. Next higher in energy for V-2(CO)(9) are three structures with single four-electron donor bridging CO groups identified by their computed v(CO) frequencies and V-O distances. The V-V distances in these three isomers suggest metal-metal single bonds. This study of V-2(CO)(9) supports the following general points: (1) Metal-metal bonds of an order higher than three are not favorable in metal carbonyl chemistry. (2) The 18-electron rule for metal carbonyls begins to break down when the metal atom, i.e., vanadium in this case, has only five valence electrons.