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[Display omitted] • An efficient and stable bi-functional electrocatalyst is developed by a facile foaming-assisted electrospinning method. • FeCo alloy nanoparticles are uniformly embedded within N-doped mesoporous carbon nanofibers. • The FeCo@NCNF electrocatalyst exhibited excellent ORR and OER performances with a smaller potential gap (ΔE) of 0.749 V. • The as-constructed Zn-air battery exhibits a larger power density of 134.83 mW cm−2 and long-term cycling stability after 216 h tests. A low-cost, efficient and durable bi-functional electrocatalysts for bi-functional oxygen reduction/evolution reactions (ORR/OER) is vital for modern energy conversion devices. Here, we report the exploration of advanced OER/ORR bi-functional catalysts based on foaming-assisted electrospinning. The addition of foaming agent is beneficial to prevent the agglomeration of FeCo alloy nanoparticles decorated on the N-doped mesoporous carbon nanofibers (FeCo@NCNF). These rationally designed electrocatalysts exhibit an excellent bi-functional electrocatalytic activity with a low reversible overvoltage of 0.749 V. The as-constructed Zn-air battery delivers a power density of 134.83 mW cm−2 and long-term cycling stability with a slight increase of 0.02 V in potential gap over 216 h at 5 mA cm−2, surpassing to most bi-functional electrocatalysts ever reported. [ABSTRACT FROM AUTHOR]