There is an urgent need for developing non-precious metal catalysts to replace Pt-based electrocatalysts for oxygen reduction reaction (ORR) in fuel cells. Atomically dispersed M-Nx/C catalysts have shown promising ORR activity; however, enhancing their performance through modulating their active site structure is still a challenge. In this study, a simple approach was proposed for preparing atomically dispersed iron catalysts embedded in nitrogen- and fluorine-doped porous carbon materials with five-coordinated Fe-N5 sites. The C@PVI-(DFTPP)Fe-800 catalyst, obtained through pyrolysis of a bioinspired iron porphyrin precursor coordinated with an axial imidazole from the surface of polyvinylimidazole-grafted carbon black at 800 °C under Ar atmosphere, exhibited a high electrocatalytic activity with a half-wave potential of 0.88 V vs. reversible hydrogen electrode for ORR through a four-electron reduction pathway in alkaline media. In addition, an anion-exchange membrane electrode assembly (MEA) with C@PVI-(DFTPP)Fe-800 as the cathode electrocatalyst generated a maximum power density of 0.104 W cm-2 and a current density of 0.317 mA cm-2. X-ray absorption spectroscopy demonstrated that a single-atom catalyst (Fe-Nx/C) with an Fe-N5 active site can selectively be obtained; furthermore, the catalyst ORR activity can be tuned using fluorine atom doping through appropriate pre-assembling of the molecular catalyst on a carbon support followed by pyrolysis. This provides an effective strategy to prepare structure-performance-correlated electrocatalysts at the molecular level with a large number of M-Nx active sites for ORR. This method can also be utilized for designing other catalysts.