In this paper, perovskite type La0.6Ca0.4CoO3 as a catalyst of oxygen reduction was prepared, and the structure and performance of the catalysts was examined by means of IR, X-ray diffraction (XRD), and thermogravimetric (TG). Mixed catalysts doped, some metal oxides were put also used. The cathodic polarization curves for oxygen reduction on various catalytic electrodes were measured by linear sweep voltammetry (LSV). A Zn–air battery was made with various catalysts for oxygen reduction, and the performance of the battery was measured with a BS-9300SM rechargeable battery charge/discharge device. The results showed that the perovskite type catalyst (La0.6Ca0.4CoO3) doped with metal oxide is an excellent catalyst for the zinc–air battery, and can effectively stimulate the reduction of oxygen and improve the properties of zinc–air batteries, such as discharge capacity, etc.