Primary lithium metal air (Li-air) batteries using aprotic organic electrolyte solutions containing methoxybenzene are reported for the first time. Methoxybenzene demonstrates an increased solubility of lithium oxide, the reduction product with an extremely low solubility that leads to cell failure due to pore blocking in the carbon cathode. Primary Li-air batteries with electrolytes containing methoxybenzene demonstrate significantly high discharge capacities than cells with electrolytes containing no methoxybenzene. Cell performance is presented for both 10 cm(2) pouch type cells and 100 cm(2) fixtured cells and the effect of electrode area is discussed. (C) 2011 The Electrochemical Society. [DOI: 10.1149/1.3596719] All rights reserved.