Preparing high-performance catalysts for oxygen reduction reaction (ORR) with low Pt loading is crucial to promote the development of clean energy storage devices such as metal air batteries. Herein, Co/N-HCMs support material with isolated Co atoms and hollow flower-like structure could be prepared by a self-sacrificing template strategy. Co/N-HCMs are then used to anchor Pt to obtain PtCo/N-HCMs catalyst with low Pt loading. Thanks to its improved specific surface area, hierarchical porous structure, and reinforced metal-support interactions, the obtained PtCo/N-HCMs deliver high onset potential of 0.99 V and half-wave potential of 0.82 V, and an excellent durability. When used as air cathode catalyst, PtCo/N-HCMs-based Zinc-air battery (ZAB) exhibits a power density of up to 202 mW cm−2, which is significantly better than ZAB assembled with commercial Pt/C. This study provides an effective strategy for preparing high-performance electrocatalysts with low precious metal content for use as the cathode of metal-air batteries.