In this paper, some of our recent research work about applications of Raman microspectrometry for the study of lithium insertion compounds is presented. The examples developed include (i) the LixV2O5 system produced either from chemical or electrochemical processes, from bulk powder and thin films electrodes; (ii) the Li/TiO2 anatase system investigated as a composite electrode. New spectroscopic data on both systems are presented, owed to a careful experimental method and a thorough theoretical analysis. This approach allows relevant information to be provided on some aspects of the electrochemical behaviour exhibited by these electrode materials. (C) 2007 Elsevier B.V. All rights reserved.