Hydrogen, as a clean energy, has broad prospects in renewable energy and environmental protect in the future. Mo2N is a promising candidate in electrocatalyzing the hydrogen evolution reaction (HER) due to its low-cost and resembled electronic properties. In this work, mesoporous Mo2N/NC composite catalysts are synthesized by polymerizing p-phenylenediamine (p-PDA) with ammonium heptamolybdate and following calcination under N-2 atmosphere. These catalysts show excellent HER performance in 0.5 M H2SO4 solution, allowing a low overpotential of 217 mV to produce H-2 at the electric current density of 10 mA cm(-2) with catalyst loading of 0.5 mg cm(-2). After 1000 cycles of acceleration degradation tests, Mo2N/ NC remains negligible overpotential losses. These stable electrochemical properties are mainly related to the strong interaction of Mo2N and NC materials, which accelerates the electron transfer further for hydrogen evolution, besides the unique mesoporous structures benefitting to the transmission of the electrolyte. This work also reveals the importance of amine's structure in synthesizing high-performance Mo2N anchored on N-doped carbon materials. (C) 2017 Elsevier Ltd. All rights reserved.