The key factor to improve the electrochemical performance of Li–O2 batteries is to find bi-functional cathode catalysts to promote the oxygen reduction and evolution reactions. Despite tremendous effects, developing cathode catalysts with high activity remains a great challenge. Herein, we report the synthesis of hierarchical macroporous/mesoporous NiCo2O4 nanosheets as an effective cathode catalyst for Li–O2 batteries. The hierarchical porous catalyst was synthesized by a hydrothermal method, followed by low temperature calcination. SEM and TEM observations clearly present that the as-prepared NiCo2O4 nanosheets showed a hierarchical porous structure with mesopores distributed through the surface of NiCo2O4 nanosheets and macropores formed between the crumpled nanosheets. When investigating as the cathode catalyst in Li–O2 batteries, the as-prepared NiCo2O4 nanosheets exhibited higher reversible capacity, lower charge/discharge overpotential, and better cycling stability than those of pristine carbon black. The enhanced electrochemical performance of NiCo2O4 nanosheets should be attributed not only to the high catalytic activity of NiCo2O4 towards oxygen reduction reaction and oxygen evolution reaction, but also to the novel hierarchical porous structure of NiCo2O4.