Non-aqueous lithium–oxygen(Li–O_2) batteries have been considered as the superior energy storage system due to their high-energy density, however, some challenges limit the practical application of Li–O_2 batteries. One of them is the lack of stable electrolyte. In this communication, a novel electrolyte with ethylene sulfite(ES) used as solvent for Li–O_2 batteries was reported. ES solvent showed low volatility and high electrochemical stability. Without a catalyst in the air-electrode of Li–O_2 batteries, the batteries showed high specific capacity, good round-trip efficiency and cycling stability. Non-aqueous lithium-oxygen (Li-O 2) batteries have been considered as the superior energy storage system due to their high-energy density, however, some challenges limit the practical application of Li-O 2 batteries. One of them is the lack of of stable electrolyte. In this communication, a novel electrolyte with ethylene sulfite (ES) used as a solvent for Li-O 2 batteries was reported. ES solvent showed low volatility and high electrochemical stability. Without a catalyst in the air-electrode of Li-O 2 batteries , the batteries showed high specific capacity, good round-trip efficiency and cycling stability.