Core-shell Fe3C@N-C nanostructures constructed by Fe3C core encapsulated in N-doped carbon nanotubes (FFCN-MP4000) is designed and readily prepared via a facile and economical solid-state chemical route. By controlling the proportion of C and N in the starting materials, the composition of Fe-N-C core-shell nanotubes was optimized, then provided more possible active sites as electrocatalysts, exhibited superior oxygen reduction performance. Onset potential (E-onset) of 0.96 V versus reversible hydrogen electrode (RHE) and half-wave potential (E-1/2) of 0.83 V vs RHE was obtained in 0.1 M KOH, which are comparable to those of the commercial Pt/C catalyst (E-onset = 0.98 V, E-1/2 = 0.84 V vs RHE). Notably, the limited current density for FFCN-MP4000 can reach to 6.6 mA cm(-2), and it efficiently catalyzes 4-electron reduction of oxygen (n = 3.98) with a hydrogen peroxide yield of below 2.2%. In addition, the methanol tolerance and durability are even superior to commercial Pt/C catalyst. This work provides a facile and economical strategy for the feasible design of oxygen reduction reaction (ORR) electrocatalyst with high activity and low cost in alternative commercial Pt/C electrocatalyst. (C) 2020 Elsevier Inc. All rights reserved.