A new polymer electrolyte comprising the blend of poly(dimethylsiloxane-co-ethylene oxide) (P(DMS-co-EO)), and poly(epichlorohydrin-co-ethylene oxide) (P(EPI-co-EO)), with different concentrations of LiClO4 is described. The polymer electrolyte was prepared by a solution-cast technique. The electrochemical properties were studied by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry techniques. The maximum ionic conductivity (σ=1.2×10−4 Scm−1) was obtained for the P(DMS-co-EO)/P(EPI-co-EO) 15/85 and 20/80 blends with 6wt.% LiClO4. These same films had a wide electrochemical stability, higher than 5V at room temperature. A stable passive layer at the interface between the polymer electrolyte and lithium metal was formed within the first few days and maintained during the follow storage period. UV-Vis absorption spectra of the blends showed a transparent polymer electrolyte in the visible region.