The lithium–oxygen battery has the potential to deliver extremely high energy densities; however, the practical use of Li‐O2 batteries has been restricted because of their poor cyclability and low energy efficiency. In this work, we report a novel Li‐O2 battery with high reversibility and good energy efficiency using a soluble catalyst combined with a hierarchical nanoporous air electrode. Through the porous three‐dimensional network of the air electrode, not only lithium ions and oxygen but also soluble catalysts can be rapidly transported, enabling ultra‐efficient electrode reactions and significantly enhanced catalytic activity. The novel Li‐O2 battery, combining an ideal air electrode and a soluble catalyst, can deliver a high reversible capacity (1000 mAh g−1) up to 900 cycles with reduced polarization (about 0.25 V).