Recently, the lithium-oxygen (Li-O2) battery has attracted much interest due to its ultrahigh theoretical energy density. However, its potential application is limited by an unstable electrolyte system, low round-trip efficiency, and poor cyclic performance. In this study, we present a new electrolyte based on N, N′- dimethylpropyleneurea (DMPU) applied for the Li-O2 battery. This electrolyte possesses high ionic conductivity and achieves a low discharge/charge voltage gap of 0.6 V, which is mainly due to the possible one-electron charge transfer mechanism. The introduction of the antioxidant butylatedhydroxytoluene (BHT) as an additive stabilizes the superoxide radical by chemical adsorption and improves the cyclic performance remarkably. Thus, this new electrolyte system may be one of the candidates for Li-O2 batteries.