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[Display omitted] • HP-Fe-N-C/2 exhibits eminent ORR activity and stability in alkaline and acidic media. • The Zn-air battery shows high power density and superior cyclability for 1342 h. • The power density of HP-Fe-N-C/2-based PEM fuel cell is up to 0.66 W cm−2. Atomically dispersed Fe-N-C catalysts are a promising alternative to platinum group metal (PGM) catalysts for oxygen reduction reaction (ORR). However, attaining efficient ORR activity and superior stability in Fe-N-C catalysts is still crucial yet challenging. Herein, we report a rational SiO 2 -mediated two-step pyrolysis strategy for stabilizing densely exposed Fe-N 4 active sites on hierarchically porous carbon (HP-Fe-N-C/2). Benefiting from the high density of accessible Fe-N 4 sites and the high graphitization degree of carbon support, the obtained HP-Fe-N-C/2 catalyst demonstrates outstanding activity and stability for ORR in both alkaline and acidic media. When used as the cathode catalyst, the assembled Zn-air battery shows a high peak power density of 217 mW cm−2 and ultra-long cycling stability for 1342 h without noticeable degradation. As a PGM-free cathode in proton exchange membrane fuel cells, it delivers a maximum output power density of 0.66 W cm−2. [ABSTRACT FROM AUTHOR]