Despite their exceptionally large specific capacities, the use of Li–O2 batteries has been limited because of their poor cycle lives, which originates from irreversible reaction processes during each cycle. Recent investigations have found that electrolyte decomposition is one of the most critical reasons for capacity decay. Herein, we report that a blended electrolyte, consisting of a carbonate solvent and an ionic liquid, improves the cycle lives of Li–O2 batteries remarkably through a synergistic effect from both components. Both electrolyte components perform complementary functions to each other: The ionic liquid suppresses the decomposition of the carbonate solvent, and the carbonate solvent resolves the poor ionic conductivity of the ionic liquid. This study confirms the importance and opportunities for the use of electrolytes in Li–O2 batteries.