V2O5 nanotubes synthesized via the sol-gel route has been studied by electron energy loss spectroscopy (EELS), x-ray absorption spectroscopy (XAS), and energy dispersive x-ray analysis, in order to understand the local structure of vanadium in the nanotubes. Contrary to our expectation, all the features of the XAS and EELS spectra of the V2O5 nanotubes are in line with that of bulk layered vanadium oxide revealing that vanadium is present in the 5+ oxidation state in the nanotubes. However, V2O5 nanotubes exhibit additional surface states in their electronic structure in comparison with bulk V2O5. A comparison of measured and calculated spectra allows us to distinguish single-wall from multiwall V2O5 nanotubes. [ABSTRACT FROM AUTHOR]