A highly active and stable electrochemical catalyst of nanoporous molybdenum carbide nanowires (np-Mo2C NWs) has been developed for hydrogen evolution reaction (HER). The np-Mo2C NWs were synthesized simply by pyrolysis of a MoOx,/amine hybrid precursor with sub-nanosized periodic structure under an inert atmosphere. The enriched nanoporosity and large reactive surface of these highly dispersed nanowires with uniform Mo2C nanocrystallites provide an efficient electrocatalysis, leading to their superior HER activity with lower onset overpotential and higher current densities than Mo2C microparticles. This study opens a new perspective for the development of highly active non-noble electrocatalysts for hydrogen production from water splitting.