The discharge/charge performance of Li-air cell using the carbon-supported LaMn0.6Fe0.4O3 nanoparticle as a cathode catalyst was investigated in this study. The carbon-supported LaMn0.6Fe0.4O3 nanoparticle was prepared via a reverse homogeneous precipitation method, and fabricated to air electrode. Li-air cell was constructed using air electrode, Li metal foil and 1.0 M LiPF6 in propylene carbonate as a cathode, anode and electrolyte, respectively. As the result, the carbon-supported LaMn0.6Fe0.4O3 nanoparticle exhibited both the oxygen evolution activity and the oxygen reduction activity in the non-aqueous electrolyte. The investigation about the presence and absence of the catalytic layer and the gas diffusion layer revealed that each layer is indispensable for the excellent electrode performance, and that the catalytic layer and the gas diffusion layer has a important role to supply the electrolyte and the oxygen gas, respectively. The investigation about the amount of the catalytic layer and the effect of the oxygen concentration revealed that the oxygen diffusability into the air electrode strongly affects to the discharge capacity of Li-air cells.