The rational design of advanced oxygen reduction reaction (ORR) catalysts is essential to improve the performance of energy conversion devices. However, it remains a huge challenge to construct hierarchical micro-/meso-/macroporous nanostructures, especially mesoporous transport channels in catalysts, to enhance catalytic capability. Herein, motivated by the characteristics of energetic metal-organic frameworks (EMOFs) that produce an abundance of gases during high-temperature pyrolysis, we prepared a unique tetrazine-based EMOF-derived electrocatalyst (denoted as Fe3C@NSC-900) consisting of highly dispersed Fe3C nanoparticles and N,S-codoped mesoporous carbon nanotubes. The mesopore-dominated core-shell structure endows Fe3C@NSC-900 with excellent catalytic activity and efficient mass transfer. Thus, optimal Fe3C@NSC-900 demonstrates a high half-wave potential of 0.922 V and great stability in 0.1 M KOH, outperforming commercial Pt/C and most of the reported ORR catalysts. As far as we know, this work is the first application of a tetrazine-based EMOF derivative for the electrocatalytic ORR and is expected to offer some constructive insights into potential of EMOFs for new-generation catalyst design.