Herein, the study reports a facile and scale-up able strategy to synthesize metal organic frameworks (MOFs) Fe-7,7,8,8-Tetracyanoquinodimethane (Fe-TCNQ) as precursors to develop non-precious metal bifunctional electrocatalysts through a one-step hydrothermal route. Then, Fe3C/carbon nitride (Fe3C@CNx) core-shell structure composites are readily available through pyrolyzing Fe-TCNQ at reasonable temperature, during which hierarchical porous structures with multimodal porosity formed. Nitrogen doped porosity carbon layers can facilitate mass access to active sites and accelerate reaction. Consequently, the optimized catalyst exhibits superior oxygen reduction reaction (ORR) electrocatalytic activity and better catalytic activity for oxygen evolution reaction (OER) in alkaline medium than that of Pt/C, which can be attributed to the synergistic effect of strong coupling between Fe3C and nitrogen doped carbon shells, active sites Fe-N-X, optimal level of nitrogen doping, and appropriate multimodal porosity. (C) 2018 Published by Elsevier B.V.