Exploring highly active non-noble metal oxygen reduction reaction (ORR) catalysts and understanding the mechanism are very essential for future energy conversion and storage devices. Herein, we provide a novel method to produce FeP nanoparticles and single atom Fe co-doped porous hollow carbon hybrids (FeP@SA-Fe/HC) from iron metal-organic framework (NH2-MIL(Fe)), phytic acid and melamine. Interestingly, thanks for the co-existence of the atomic Fe and FeP nanoparticles, porous hollow microstructure, and heteroatom doping, the obtained FeP@SA-Fe/HC-900 hybrid shows very high ORR activity with a more positive half-wave potential of 0.843 V (vs. reversible hydrogen electrode) in 0.10 M KOH, comparing with the commercial 20 wt% Pt/C catalyst (0.807 V). Our methodology puts forwards a new sight to enhance the electrochemical catalytic performance of carbon composite materials through the synergistic effect of the atomic-metal and metal nanoparticles. (C) 2020 Elsevier Inc. All rights reserved.