Exploring highly active, stable, and inexpensive electrocatalysts for the oxygen reduction reaction (ORR) is pivotal in developing high-performance energy conversion devices. Moreover, the production of catalysts containing transition metals with the appropriate nitrogen doping level is a potential approach to increase ORR catalytic efficiency, especially under acidic conditions. In this study, a hierarchical graphitic porous carbon-containing Fe and N was obtained via pyrolysis of a bimetal MOF (Fe/ZIF-8) composited with pyrrole. Further experimental and theoretical results confirmed that the synergistic effects between Fe-based nanoparticles and N-doping in the networks are likely form one of the main reasons for better ORR performance. Under optimized conditions, the resultant Fe-bNCNT/NC-900 (iron-based nanoparticles enwrapped in bamboo-like nitrogen-doped carbon nanotubes (bNCNTs) grown on N-doped sheet-like carbon) exhibits high electrocatalytic activity, high selectivity (direct 4e– reduction of oxygen to water), and stability in both acidic and alkaline electrolytes. Under acidic conditions, the half-wave potential (E1/2 = 0.770 VRHE) of Fe-bNCNT/NC-900 is comparable to commercial Pt/C (E1/2 = 0.800 VRHE). However, this catalyst shows better activity with a half-wave potential of 0.920 VRHE, which is more than Pt/C (E1/2 = 0.880 VRHE) in an alkaline electrolyte. The E1/2 of Fe-bNCNT/NC-900 under acidic and alkaline conditions experienced a 170 and 28 mV loss after 20 000 continuous cycles, and these results show the prepared catalyst has promising stability.