Oxygen reduction reaction (ORR) is the key reaction in various electrochemical energy devices. This work reports an inexpensive mesoporous LaMnO3+δ perovskite for ORR with remarkable activity, synthesized by a facile aerosol-spray assisted approach. The mesoporous LaMnO3+δ material shows a factor of 3.1 higher activity (at 0.9V vs. RHE) than LaMnO3 obtained from co-precipitation method (LMO-CP). Based on results of x-ray absorption near-edge spectroscopy (XANES), x-ray photoelectron spectroscopy (XPS) and Brunauer–Emmett–Teller (BET) analysis, we conclude that the chemical state of surface Mn and the high surface area are the sources to the notably enhanced activity. The study of Zn-air batteries device further confirmed a Pt/C comparable performance in the practical devices with the novel mesoporous LaMnO3+δ catalyst, where the power density at 200mA/cm2 is only 2.1% lower than in the battery with same-loaded Pt/C catalyst. Therefore, the high mass activity and low-cost of Mn/La may make LaMnO3+δ further approach to the application of electrochemical devices.