Production of nonprecious catalysts with high electrocatalytic activity is one of the promising paths to drive fuel cells' commercialization. Herein, we present rational tuning to prepare metal-organic framework (MOF)-derived nonprecious catalysts. Nanoporous MOF-derived catalysts were hierarchically prepared by using functional carbon black assembled with Material Institut Lavoisier (MIL)-101(Fe) as a precursor, followed by nitrogen doping and carbonization by pyrolysis. The resulting catalysts contained iron and iron carbide nanoparticles encapsulated in the nitrogen-enriched mesoporous carbons, which were connected to functional carbon black (Fe/Fe3C@NC). The hierarchical structure led to electron conductivity improvement, higher active site exposure, and stronger synergistic effects. The optimal catalyst exhibited superior oxygen reduction reaction (ORR) activity with onset and half-wave potentials of 0.85 and 0.70 V vs RHE, respectively. Furthermore, it showed much higher stability and better methanol tolerance than those of the state-of-the-art Pt/C. This could offer a practical approach to synthesizing nonprecious catalysts with high ORR activity for fuel cell applications.