Confocal Raman microspectrometry has been applied to the characterization of a lithium battery involving pure lithium metal at the anode, the polymer electrode P(EO)(20), LiN(SO2CF3)(2) and V2O5 as active cathode material. Twenty points have been simultaneously analyzed on a line perpendicular to the two electrodes during cycling. The spectra reveal salt concentration gradients in the electrolyte, the presence ofpolluting species at the Li/electrolyte interface and structural changes of vanadium oxide.