Polymer electrolytes represent the ultimate in terms of desirable properties for the next-generation of safe and efficient energy storage and production devices, because they can offer an all-solid-state construction, a wide variety of shapes and sizes, light-weight, low-cost of fabrication, high safety and a higher energy density. Free radical photo-polymerization (UV-curing) is an interesting process to produce polymer electrolytes. It takes place at ambient temperature: a liquid polyfunctional monomer, containing a proper photo-initiator, forms a cross-linked film upon UV irradiation. It appears highly advantageous, due to its easiness and rapidity in processing, very short time with high efficiency and eco-friendliness as the use of solvent is avoided. In this communication, we offer a summary of our recent and most interesting results regarding the synthesis, physico-chemical and electrochemical characterization of polymer electrolyte membranes based on different monomers/oligomers (methacrylic and/or ethylene oxide based) with several kinds of additives, salts, plasticizers and fillers. Also room temperature ionic liquids (RTIL) may be in-situ incorporated into the membranes to improve safety as well as environmental impact. Different kinds of eco-friendly bio-based additives (e.g., nanocellulose, caffeine, chitin, etc.) are considered in order to outstandingly improve mechanical, interfacial and electrochemical properties of the polymer electrolytes. The results shown here demonstrate that, compared to other techniques, UV curing is a versatile method, easy to be scaled-up at an industrial level due to its easiness and rapidity in processing. It can open up promising perspectives in obtaining innovative electrolytes with high flexibility, well suited for flexible and/or non-planar electronics application