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 MoO_x/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.