Co-doped perovskite oxide La0.4Sr0.6CoxMn1-xO3(x=0, 0.2, 0.4) composites are prepared by sol-gel method utilizing citric acid as chelating agent. These composites show good catalytic activities when tested as catalysts rechargeable lithium-air batteries. In particular, the La0.4Sr0.6Co0.4Mn0.6O3 shows a lower potential gap. When these samples are tested as catalysts for Li-air batteries at a current density of100 mA g-1, the discharge capacities with different La0.4Sr0.6CoxMn1-xO3(x=0,0.2, 0.4) catalysts are 5819, 6420, and 7227 mA h g-1,respectively. In addition, under a capacity limitation of 1000 mA h g-1, the cell using La0.4Sr0.6Co0.4Mn0.6O3 as catalyst shows good cycling stability up to 46 cycles. The good electrochemical performance suggests that suitable doping of Co in Mn site of La0.4Sr0.6MnO3 could be a promising route to improve the catalytic activity.