Single nanocrystalline tungsten carbide (WC) was first synthesized on the tips of vertically aligned carbon nanotubes (VA-CNTs) with a hot filament chemical vapor deposition (HF-CVD) method through the directly reaction of tungsten metal with carbon source. The VA-CNTs with preservation of vertical structure integrity and alignment play an important role to support the nanocrystalline WC growth. With the high crystallinity, small size, and uniform distribution of WC particles on the carbon support, the formed WC–CNTs material exhibited an excellent catalytic activity for hydrogen evolution reaction (HER), giving a η10 (the overpotential for driving a current of 10 mA cm–2) of 145 mV, onset potential of 15 mV, exchange current density@ 300 mV of 117.6 mV and Tafel slope values of 72 mV dec–1 in acid solution, and η10 of 137 mV, onset potential of 16 mV, exchange current density@ 300 mV of 33.1 mV and Tafel slope values of 106 mV dec–1 in alkaline media, respectively. Electrochemical stability test further confirms the long-term operation of the catalyst in both acidic and alkaline media.