<p>Li-O₂ cells with high theoretical energy density are considered the next-generation electrochemical energy storage device. A complex electrochemical environment under O₂ conditions hinders the further development of the Li-metal anode in Li-O₂ cells. The composition of the solvent in the electrolyte has a significant impact on the electrochemical performance of Li-metal under an O₂ atmosphere. Herein, the compatibility of typical diglyme (G2), triglyme (G3), and tetraglyme (G4) ether-based solvents with Li-metal anode in O₂ environment is comprehensively unraveled from the perspective of both Li/Li symmetric cells in a harsh O₂ environment and Li-O₂ cells. Electrolyte with G2-based solvent can promote the formation of a thin and uniform solid electrolyte interphase (SEI) film, facilitating dendrite growth suppression and rechargeability of Li/Li symmetric cells under O₂ atmosphere. However, its poor oxidative stability under high voltage impedes further long-term cycling of the Li-O₂ cell. The evolution of SEI film with fragmentation accumulation and reconstruction during cycling leads to poor reversibility of both Li/Li symmetric cells and Li-O₂ cells in G3-based electrolyte. In G4-based electrolyte, a relatively uniform SEI film and side reaction suppression resulting from the oxidative stability of the electrolyte together contribute to long-term stable cycle life of Li-O₂ cells. Therefore, among three ether-based solvents (G2, G3, and G4), G2 is more effective in enhancing the reversibility of Li/Li symmetric cell under O₂-rich conditions, while G4 is more conducive to the rechargeability of Li-O₂ cell. This work provides new insights for suitable solvent selection of stable Li-metal anode under O₂ environment and has also paved a novel research avenue for other metal-based batteries in a harsh O₂ atmosphere.</p>