Metal nitrogen-carbon catalysts have become a promising alternative to platinum-based catalysts in fuel cells due to their high stability and platinum-like activity. However, the corrosion and deactivation of active sites in the solution still restrict the inherent reaction kinetic rate. For this reason, it is important to stabilize the catalyst through a controllable doping strategy to obtain high activity catalysts for oxygen reduction reactions (ORR). Herein, the pyrolysis strategy is demonstrated in the synthesis of iron-based catalysts co-doped with nitrogen and biomass-derived phosphorus (denoted as N, P-Fe/C), and the pore size of the catalyst is mostly distributed at 1 nm or 50 nm, respectively. The half-wave potential (0.893 V) and the current density (4.05 mA cm−2) at 0.85 V of the catalyst exceed those of the commercial Pt/C. The remarkable ORR performance can be attributed to its distinct hierarchical pore structure, the modulation effect of nitrogen and phosphorus co-doping on the carbon matrix, and the combined effect of the FeNx active sites, which improves the accessibility of reactants and accelerating the absorption/desorption of the reaction intermediate, thereby increasing reaction rates. And N, P-Fe/C has great potential as a promising substitute for platinum-based catalysts.