Multiporous MnCo2O4 microspheres are fabricated via the solvothermal method followed by pyrolysis of carbonate precursor to demonstrate excellent bifunctional catalytic activity toward both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Because of this multiporous structure, the resulting MnCo2O4 microspheres show an efficient electrocatalytic performance in LiTFSI/TEGDME electrolyte-based Li鈥揙2 batteries. MnCo2O4 microspheres as the air cathode deliver better performance during the discharging and charging processes and good cycle stability compared with that of the Super P. This preliminary result manifests that multiporous MnCo2O4 microspheres are promising cathode catalysts for nonaqueous Li鈥揙2 batteries.