A novel electrolyte with chloromethyl pivalate (CP) used as solvent was first reported for non-aqueous lithium-oxygen (Li-O2) batteries. Since there are no α-H atoms in the structure of CP, the CP based electrolyte in both superoxide radical solution and real Li-O2 battery environment showed good chemical stability against superoxide radicals, which was confirmed by 1H NMR and 13C NMR measurements. Without a catalyst in the cathode of Li-O2 batteries, the batteries showed high specific capacity and cycling stability.