In this presentation we describe the preparation of solvent-free solid polymer electrolytes (SPEs) by the sol–gel route with the incorporation of controlled quantities of lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) into the host matrix. The host framework of these xerogels, designated as di-ureasils and represented by d-U(900), contains oxyethylene oligomers with about 15 repeat units bonded at each end to a siliceous backbone through urea bridging links. Electrolytes were characterized by ionic conductivity measurements, cyclic voltammetry at a gold microelectrode and thermal analysis. The results obtained reveal that these hybrid materials are completely amorphous and exhibit appropriate electrochemical characteristics for a variety of applications.