Molybdenum carbide is considered to be one of the most competitive catalysts for hydrogen evolution reaction (HER) regarding its high catalytic activity and superior corrosion resistance. But the low electrical conductivity and poor interfacial contact with the current collector greatly inhibit its practical application capability. Herein, carbon nanotube (CNT) supported molybdenum carbide was assembled via electrostatic adsorption combined with complex bonding. The N-doped molybdenum carbide nanocrystals were uniformly anchored on the surfaces of amino CNTs, which depressed the agglomeration of nanoparticles while strengthening the migration of electrons. The optimized catalyst (250-800-2h) showed exceptional electrocatalytic performance towards HER under both acidic and alkaline conditions. Especially in 0.5 M H2SO4 solution, the 250-800-2h catalyst exhibited a low overpotential of 136 mV at a current density of 10 mA/cm2 (η10) with the Tafel slope of 49.9 mV dec−1, and the overpotential only increased 8 mV after 20,000 cycles of stability test. The active corrosive experiment revealed that more exposure to high-activity γ-Mo2N promoted the specific mass activity of Mo, thus, maintaining the catalytic durability of the catalyst.