Vanadium oxide clusters, (V2O5)(n), have been predicted to possess interesting polyhedral cage structures, which may serve as ideal molecular models for oxide surfaces and catalysts. Here we examine the electronic properties of these oxide clusters via anion photoelectron spectroscopy for (V2O5)(n)(-) (n = 2-4), as well as for the 4d/5d species, Nb4O10- and Ta4O10-. Well-resolved photoelectron spectra have been obtained at 193 and 157 nm and used to compare with density functional calculations. Very high electron affinities and large HOMO-LUMO gaps are observed for all the (V2O5)(n)(-) clusters. The HOMOLUMO gaps Of (V2O5), all exceeding that of the band gap of the bulk oxide, are found to increase with cluster size from n = 2-4. For the M4O10 clusters, we find that the Nb/Ta species yield similar spectra, both possessing lower electron affinities and larger HOMO-LUMO gaps relative to V4O10. The structures of the anionic and neutral clusters are optimized; the calculated electron binding energies and excitation spectra for the global minimum cage structures are in good agreement with the experiment. Evidence is also observed for the predicted trend of electron delocalization versus localization in the (V7O7)(n-) clusters. Further insights are provided pertaining to the potential chemical reactivities of the oxide clusters and properties of the bulk oxides.