Today, special interest is focused on polymer systems showing high ionic conductivity at ambient and/or sub ambient temperatures, since they find unique practical applications, such as separators in high power, versatile, rechargeable Li-based batteries. Thermo-set membranes prepared by free radical photo polymerisation (UV-curing) could be an interesting alternative to existing polymer electrolytes. In the present paper, we report the application of this technique to the synthesis of gel-polymer membranes which can be used as electrolytes for lithium battery application. These membranes are prepared by mixing a dimethacrylic (BEMA) and/or a diacrylic monomer (PEGDA), a methacrylic reactive diluent (PEGMA) and a radical photo-initiator with the in situ addition of a EC/DEC solution. The above mixtures are UV irradiated to obtain transparent, flexible, easy to handle gel-polymer films. The gel-polymer electrolytes (GPEs) are then prepared by swelling these membranes in different liquid electrolytes. The results obtained indicate some superior and satisfactory performances in terms of ionic conductivity at ambient temperature for various GPEs prepared with different lithium salt solutions. The relevance of these features in view of practical application is here demonstrated by the response of lithium cells based on prepared GPEs.