Non-aqueous lithium air batteries with high energy density have been regarded to be the most attractive contender in the future energy storage techniques. Herein, the perovskite La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) nanoparticles are studied as the cathode catalyst for non-aqueous lithium air batteries. The results confirm that nanostructured LSCF exhibits admirable electrochemical activity and can effectively reduce the overpotential. Batteries with LSCF catalyst can increase the discharge capacity from 9678mAhg−1 to 13979mAhg−1 and improve the cycle stability from 10 cycles to 20 cycles at 200mAg−1. The study reveals that the formation and decomposition processes of Li2O2 can be effectively promoted by the introduction of LSCF nanoparticles. The possible catalytic mechanism of LSCF in reducing overpotential is also proposed.