Structure and vibrational dynamics of -V2O5 synthesized from a pristine -LiV2O5 sample via a chemical oxidation route was studied by means of Raman spectroscopy and quantum-chemical calculations. The calculations based on density functional theory reliably reproduce the experimental structure of the -V2O5 lattice. The calculated Raman spectrum agrees remarkably well with the experimental one. Making use of the agreement, a complete assignment of Raman bands to vibrations of particular structural units is proposed. The comparison of Raman spectra and structural features of -V2O5 and -V2O5 polymorphs allowed establishing reliable structure-spectrum' correlations and identifying Raman peaks characteristic for different structural units. Copyright (c) 2015 John Wiley & Sons, Ltd.