Transition metal carbides have been widely developed as bifunctional electrocatalysts for water splitting due to their attractive superiority, however, the further environment of their performance still remains a significant challenge. Herein, a novel hierarchical hybrid of Fe3C nanoparticles and carbon nanofibers supported N-doped carbon framework (Fe3C@CNF/NC-950 °C) was developed by in situ high-temperature pyrolysis. The introduction of tripolycyanamide induced the formation of carbon nanofibers (CNF), fabricating the hierarchical architecture of 1D CNF and 2D carbon framework. Benefiting from the integration of multicomponent active phases, including Fe3C nanoparticles, carbon nanofibers and N-doped carbon framework, Fe3C@CNF/NC-950 °C hybrid electrode presents remarkable electrocatalytic performances toward both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), as well as robust durability, highlighting Fe3C@CNF/NC-950 °C as promising alternative of noble-metal-based materials.