Rational designing and exploiting non-noble metal electrocatalysts with desirable nanoarchitecture and abundant active sites are crucial but challenging requirements for the development of fuel cells and Zn-air batteries (ZABs). Herein, a highly efficient carbonous hybrid is developed using a facile and effective synthesis strategy via template-assisted and optimized post-pyrolysis processes. The optimized electrocatalyst (denoted as Fe@NC-700) has extremely large specific surface area (1262.8 m² g^–1), and presents a desirable hierarchically porous nanoarchitecture, including plenty micro-/meso-pores, which endows the catalyst with the enhanced mass transfer for the reaction species. More importantly, Fe@NC-700 possesses not only numerous Fe^IIN₄ moiety uniformly dispersed in N-doped carbon matrix, but also encapsulated Fe/Fe₃C nanoparticles, synergistically boosting the electrocatalytic activity towards oxygen reduction reaction (ORR) verified by density functional theory (DFT) calculation. Due to the beneficial microstructure and rich active sites, the catalyst has a positive half-wave potential (E_1/2) of 0.865 V for ORR in alkaline electrolyte, intrinsic 4e^– reaction path and robust stability (only 14 mV negative shift of E_1/2 after 10000 potential cycles), outperforming the Pt/C. Impressively, the aqueous and quasi-solid-state primary ZABs assembled with Fe@NC-700 as cathode catalyst demonstrate superior discharge performance and excellent durability, holding promising potential in practical application of energy conversion devices.