We present a comparative structural -vibrational study of nanostructured systems of V2O5: nano-urchin (VONURs) which are spherical structures composed of a radially oriented array of VOx nanotubes (VOxNTs) with a volumetric density of similar to 40 sr(-1), and vanadium oxide nanorods (VOx-NRDs) with an average length of similar to 100 nm. The Raman scattering spectrum of the nano-urchin exhibits a band at 1014 cm(-1) related to the distorted gamma conformation of the vanadium pentoxide (gamma-V5+). The infrared vibrational spectra of the nanorods sample also exhibit a distorted laminar V2O5 structure with evidence observed for quadravalent V4+ species at 921 cm(-1). (c) 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.