We report on the microstructural changes of amorphous V2O5 films with lithium intercalation. The Raman spectra of as-deposited films show two broad peaks around at 520 and 650 cm(-1), due to the stretching modes of the V-3-O and V-2-O bonds, respectively, and a relatively sharp peak at 1027 cm(-1) due to the V5+ = O stretching mode of terminal oxygen atoms. In addition, there is a peak at 932 cm(-1) that we attribute to the V4+ = O bonds. Comparison of the Raman spectra of V2O5 films with different oxygen deficiencies confirms this assignment. This Raman peak due to the stretching mode of the V4+ = O bonds develops and shifts toward lower frequencies with increasing lithium concentration. Comparison to results from gasochromic hydrogen insertion indicates that the 932 cm(-1) Raman peak is not a result of vibrations which involve Li or H atoms. We propose that the V4+ = O bonds are created by two different mechanisms: a direct conversion from V5+ = O bonds and the breaking of the single oxygen bonds involving V4+ ions. (C) 2003 Elsevier B.V. All rights reserved.