Rechargeable lithium-air batteries have the potential to provide approximate to 3 times higher specific energy of fully packaged batteries than conventional lithium rechargeable batteries. However, very little is known about the oxygen reduction reaction (ORR) and oxygen evolution in the presence of lithium ions in aprotic electrolytes, which hinders the improvement of low round-trip efficiencies of current lithium-air batteries. We report the intrinsic ORR activity on glassy carbon (GC) as well as polycrystalline Au and Pt electrodes, where Au is the most active with an activity trend of Au >> GC > Pt. Rotating disk electrode (RDE) measurements were used to obtain the kinetic current of the ORR and the reaction order with respect to oxygen partial pressure in 1 M LiClO4 propylene carbonate: 1,2-dimethoxyethane (1:2 v/v). In addition, air electrodes with Vulcan carbon or Au or Pt nanoparticles supported on Vulcan were examined in Li-O-2 single cells, where the observed discharge cell voltages follow the catalytic trend established by RDE measurements. The ORR mechanism and the rate-determining steps were discussed and contrasted with the ORR activity trend in acid and alkaline solutions. (C) 2010 The Electrochemical Society. [DOI: 10.1149/1.3462981] All rights reserved.