Recent studies have clearly demonstrated that cyclic and linear carbonates are unstable when used in rechargeable Li–air batteries employing aprotic solvents mostly due to the cathodic formation of superoxide during the oxygen reduction reaction. In particular, it has been ascertained that nucleophilic attack by superoxide anion radical, O2 − , at O-alkyl carbon is a common mechanism of decomposition of organic carbonates. Moreover, theoretical calculations showed that ether chemical functionalities are stable against nucleophilic substitution induced by superoxide. Aim of this study is to report on a new electrolyte solution for Li–air battery formed by a mixture of an ether-based aprotic solvent with an ionic liquid (IL). The IL-based electrolyte was obtained by mixing the pure ionic liquid N-methyl-(n-butyl) pyrrolidinium bis(trifluoromethane sulfonyl) imide (here denoted as PYR14TFSI) to a 0.91M solution of lithium triflate (LiCF3SO3) in tetra ethylene glycol dimethyl etcher (TEGDME). We observed that the presence of IL beneficially affects the kinetics and the reversibility of the oxygen reactions involved at the cathode. The most significant result being a lower overvoltage for the charge reaction, compared to a Li/air cell containing the same electrolyte solution without IL.