The Li–O2 battery holds great promise as an ultra-high-energy-density device. However, its limited rechargeability and low energy efficiency remain key barriers to its practical application. Herein, we demonstrate that the ideal electrode morphology design combined with effective catalyst decoration can enhance the rechargeability of the Li–O2 battery over 100 cycles with full discharge and charge. An aligned carbon structure with a hierarchical micro-nano-mesh ensures facile accessibility of reaction products and provides the optimal catalytic conditions for the Pt catalyst. The new electrode is highly reversible even at the extremely high current rate of 2 A g−1. Moreover, we observed clearly distinct morphologies of discharge products when the catalyst is used. The effect of catalysts on the cycle stability is discussed.