The HeI/HeII photoelectron spectra of oxovanadium triethoxide (I) and oxovanadium triisopropoxide (II) are reported for the first time. We have observed significant differences in the electronic structure of the title molecules compared to their titanium analogues. Metal alkoxides (containing Mo, W, V, Nb) are precursors of polyoxometalates which are capable of supporting reversible redox reactions in the solid state. Vanadium alkoxides contain high lying occupied valence orbitals with metal character which explains the ability of their derivative polyoxometalates to become involved in reversible redox reactions. (C) 2009 Elsevier B. V. All rights reserved.