The mechanism of Fe-N/C catalysts in oxygen reduction reactions is critical to the development of efficient, sustainable non-noble metal catalysts in polymer electrolyte membrane fuel cells, but it is still in controversy. In order to understand the relationship between composition and the nanostructure of material and the electrochemical activity, this study developed a type of Fe-N/C catalyst with high electrochemical activity, which contained Fe-N_x active sites and Fe/Fe₃C nanocrystals encapsulated with nitrogen-doped carbon nanotubes. Despite being free of precious metals, the as-prepared catalyst displays high oxygen reduction reactions (ORR) activity in alkaline medium with the half-wave potential of 0.86 V(vs RHE), the mass activity of 18.84 A/g at 0.77 V(vs RHE), and the maximum current density of -4.3 mA·cm ^-2. Meanwhile, the electron transfer number is 3.7 at 0.2 V(vs RHE), revealing that the 4-electron ORR reaction exists in the catalyst. The excellent electrochemical activity is attributed to the graphene-encapsulated metallic Fe/Fe₃C nanocrystals which improves the conductivity after the growth of N-doped carbon nanotubes, and the relatively high proportion of Fe-N_x active sites distributed on the surface of Fe/Fe₃C nanoparticles. This study provides a certain reference and basis for the further study of non-noble metal catalyst and their wide application in commercial production.