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 Li x V2O5 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.