Developing low‐cost, high‐activity, and stable carbon catalysts for electrochemical oxygen reduction reaction (ORR) has become the focus for the commercialization of Zn–air batteries. Herein, the 3D stereo ferrocene is introduced for constructing a novel structure with Fe, N‐doped chrysanthemum‐like carbon microspheres. This structure consists of open nanotubes with abundant cavities, which can facilitate the exposure of active sites. Ferrocene, with a unique sandwich structure, not only plays a pivotal role in inducing the chrysanthemum‐like structure but is also involved as iron‐related active species after pyrolysis. Eventually, FCN@F‐1 exhibits outstanding ORR performance with an onset potential of 1.03 V and a half‐wave potential of 0.87 V in alkaline media, which is superior to commercial Pt/C. The durability and methanol tolerance of FCN@F‐1 also outperform those of Pt/C. In addition, the Zn–air battery assembled by FCN@F‐1 air cathode manifests an open‐circuit voltage of 1.48 V, a prominent peak power density of 132 mW cm−2, and excellent discharge platforms at different current densities, which can provide wide prospects for the development of Zn–air batteries.