Hierarchical porous iron and nitrogen co-doped carbons (HP–Fe–N–Cs) as efficient cathode catalysts for oxygen reduction reaction (ORR) in neutral media are reported. The HP–Fe–N–Cs are prepared by using polypyrrole as nitrogen source and poly(vinyl alcohol) (PVA) hydrogel-based composites as in-situ templates. In studying the effect of the iron and the hierarchical porous structure on the nitrogen-doped carbon support for ORR, we find that HP–Fe–N–Cs show more positive onset potential, higher cathodic current density, and higher electron transfer number for the ORR in neutral media than iron-free hierarchical porous nitrogen-doped carbon (HP–N–C) and non-hierarchical porous iron and nitrogen co-doped carbon (Fe–N–C), highlighting the importance of the iron and the hierarchical porous structure for improving the ORR performance. Furthermore, HP–Fe–N–Cs show better durability than the commercial Pt/C catalysts in neutral media, and the microbial fuel cells (MFCs) equipped with HP–Fe–N–Cs catalysts on cathodes exhibit comparable power outputs with those of MFCs with commercial Pt/C cathode catalysts.