Amorphous and crystallized Tin-based Composite Oxides (TCOs) thin layers as well as very thin metallic films were elaborated by r.f. sputtering. TCOs thin layers were characterized by means of XRD and XPS, Electrochemical results of TCOs-based thin film electrodes are presented. For metallic thin films, especially gold layers, the alloying de-alloying process with lithium was checked by means of XRD at different electrochemical stages. Very thin gold anodes were found to present high capacity density (3400 mA h/cm(3)) associated to a very negative and narrow voltage window.