The non-aqueous lithium oxygen battery has been considered as one of the most promising energy storage systems owing to its potentially high energy density, exceeding that of any other existing storage system for storing sustainable and clean energy. The success of Li-O2 batteries could efficiently reduce greenhouse gas emissions and the consumption of non-renewable fossil fuels. How to achieve high round-trip efficiency, high capacity, and satisfactory cycling performance, however, is still a great challenge for the lithium oxygen battery. Thus, this report will point out what factors will affect the electrochemical performance and will aim to describe how to increase the electrochemical performance by air electrode optimization. Based on recent achievements, several approaches to solving this problem, such as synthesizing electrocatalysts with high catalytic activity and designing appropriate air electrode structures, are described in details. Also, recent progress associated with novel air electrode designs and understanding the reaction process is discussed.