La1–xSrxMnO3 perovskite oxides are promising electrocatalysts for LiO2 batteries because of their excellent intrinsic catalytic activity for oxygen reduction reaction (ORR). However, the relatively inert catalytic activity for oxygen evolution reaction (OER) suppresses their practical applications in LiO2 battery. Here, nanoscale NiCo2O4 (NCO) layer with high OER catalytic activity has been homogenously incorporated into the surface of La0.8Sr0.2MnO3 (LSM) nanorods to form a core-shell structure. In this typical structure, the ORR mainly occurred on the LSM core, while the OER mainly occurred on the nanoscale NCO shell, and structure damage of catalysts coming from gas evolution can be greatly avoided. The synergy of high catalytic activity and core–shell structure results in the LiO2 battery with good rate capability and excellent cycle stability, which sustains 80 cycles without capacity attenuation at a high current density of 200 mA g−1.