It is important to fabricate iron-based nitride/conductive material composite to obtain good catalytic performance. In this work, Fe2N nanoparticles with diameter of approximately 30 nm have been successfully dispersed on the surface of nitrogen-doped graphite oxide (NrGO) by a facile sol–gel method and further ammonia atmosphere treatment. XPS, XRD, Raman, and TEM proved that Fe2N nanoparticles are well monodispersed, and nitrogen atoms are doped in NrGO. The composite possessed two merits, that is, the more catalytic active site in Fe2N nanoparticles due to the well monodispersion, and fast electron transfer due to the nitrogen dope in rGO. With the proper ratio, the composite exhibited brilliant catalytic activity and durability in acidic media. It possesses overpotential of 94 mV to approach 10 mA/cm2, a small Tefel slope of 49 mV/dec, and maintains the good electrocatalytic activity for 10 h. Cyclic voltammetry and electrochemical impedance spectroscopy indicated that the electrocatalyst possessed high catalytic active area and fast electron transfer. Our work may provide a new avenue for the preparation of low-cost iron-based nitride/NrGO composite for highly efficient electrochemical hydrogen evolution.