The delta phase of Li0.95V2O5 was prepared using a chemical intercalation reaction at ambient temperature, and the epsilon and gamma phases were obtained from thermal treatment of the delta phase. Differential scanning calorimetry (DSC) and powder X-ray diffraction were employed to characterize the three phases. The IR and Raman spectra of V2O5 and the three lithiated phases were recorded at room temperature. Factor group analysis of the normal vibrational modes was used to interpret the spectra. Raman and IR spectra from 1100 to 400 cm(-1) indicate that the epsilon phase is more structurally similar to the gamma phase than the delta phase. However, significant spectral differences between the epsilon and gamma phases are seen in the Raman spectra in the region 400-100 cm(-1). The results show that vibrational spectroscopy is a powerful tool for distinguishing the delta, epsilon and gamma phases of lithium vanadium pentoxides.