A composite cathode including N-rGO with homogeneously dispersed perovskite La_0.8Sr_0.2Co_0.8Fe_0.2O₃ on the surface is studied. Li–O₂ batteries with LSCF@N-rGO cathode show better performance than those with LSCF-SP or N-rGO cathode. EIS and morphology analysis indicate that LSCF is beneficial to remold the shape of Li₂O₂ and catalyze the decomposition of Li₂O₂.