A new polymeric solid electrolyte based on a PEO/PMVE-MAc blend, complexed with LiCiO(4), was obtained and characterized by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), polarized light optical microscopy, electrochemical impedance and cyclic voltammetry. DSC traces indicated miscibility for all the PSE samples. Crystallinity was suppressed for samples with LiCiO(4) concentrations higher than 2.5 wt%. FTIR associated with DSC studies indicated that there is a preferential formation of complexes PEO/Li+/PMVE-MAc in all PSE samples studied here. The ionic conductivity of PSE reaches a maximum of about 10(-5) S/cm at ambient temperature and 7.5 wt% LiCiO(4). The electrochemical stability window is 4.5 V and associated with the other characteristics, make the PSE studied here suitable for applications in 'smart-windows', batteries, sensors, etc.