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The concept of green in a battery involves the chemical nature of electrodes and electrolytes as well as the economic sustainability of the cell. Although these aspects are typically discussed separately, they are deeply interconnected: indeed, a new electrolyte can allow the use of different cathodes with higher energy, lower cost or more pronounced environmental compatibility. We focus on alternative class of electrolyte solutions for lithium batteries formed by dissolving LiX salts in glyme solvents, i.e., organic ethers with the molecular formula CH3O[CH2CH2O]nCH3 differing by chain length. The advantages of these electrolytes are illustrated in terms of flammability, stability, toxicity, environmental compatibility, cell performances and economic impact. A particular light is shed on the stability of these systems, particularly in the polymer state, and in various environments including oxygen, sulfur and high-energy lithium metal. The most relevant studies on the chemical-physical features, the characteristic structures, the favorable properties, and the electrochemical behavior of the glyme-based solutions are discussed, and the most recent technological achievements in terms of cell design and battery performance are described. The use of glyme-based electrolytes in high-energy cells arranged by coupling the lithium-metal anode with conventional insertion cathodes as well as in alternative and new batteries exploiting the Li-S and Li-O2 conversion processes are described in detail. The paragraphs reveal bonuses, including safety, low cost and sustainability, that can be achieved by employing the glyme-based electrolytes with respect to the commercially available ones, in particular taking into account future and alternative applications. Particular relevance is given by the glymes with long chain that reveal a remarkable stability, high safety and very low toxicity.