The electrochemical behavior of vanadium oxide V2O5 and bismuth doped manganese oxide Bi–MnO2 as battery materials was studied with a cavity microelectrode (CME). This technique, which allows working on a very few amount of material, appears to be suitable when high scan rates are used. Thus, it is possible to perform many hundreds cycles in a short time. The performances of pure vanadium oxide as lithium insertion material in inorganic media, examined with a CME appear to be excellent whereas poor results were obtained with Bi doped MnO2, for which the electrochemical mechanism proceeds via dissolution.