In situ Raman spectra of gamma-LixV2O5 were recorded using a specially constructed spectroelectrothemical cell. A 1 M solution of LiClO4 in propylene carbonate-dimethyl carbonate was used as the electrolyte and lithium foil as the anode. Three phases, gamma＇, gamma, and zeta-LixV2O5, are observed with increasing lithium content. The evolution of the Raman spectra are used to monitor the rearrangements of the V-O pyramids. The Raman bands are assigned in terms of the motions of edge-sharing, corner-sharing, and double-bonded oxygen atoms. In situ Raman spectroscopy is shown to be a potential technique for characterizing structural changes of intercalation compounds accompanying charge/discharge processes.