Tungsten carbide (WC) is an alternative to the costly and resource-constrained Pt-based catalysts. Herein, a one-step facile and easily scalable approach is reported to synthesize ultrafine WC nanocrystals encapsulated in porous N-doped carbon nanospheres (NC) by simple self-polymerization, drying, and annealing. It is worth mentioning that this developed method has four novel features: (1) the synthesis process, without any hard template or hydrocarbon gas feeding, is, notably, very facile and efficient with low cost; (2) the carbon coating on WC nanocrystals not only restrains coarsening of particles but also creates strong coupling interactions between the nanocrystallines and the conductive carbonaceous matrix; (3) uniform grape-like WC@NC nanospheres with high specific surface area can be obtained in a large scale; and (4) single-phase WC can be achieved. As a result, WC@NC demonstrates remarkable hydrogen evolution reaction (HER) electrocatalytic performance with overpotentials of 127 and 141 mV at a current density of 10 mA cm and Tafel slopes of 56.3 and 78.7 mV dec in acid and alkaline media, respectively. Our density functional theory calculations manifest that the strong synergistic electronic effect between WC and its intimately bonded carbon shell vastly boosts the HER electrocatalytic activity. WC@NC catalysts as a cathode are further tested in a home-made electrolyzer with 0.78 A cm achieved at a cell voltage of 2 V at 80 °C and operated stably at 200 mA cm for more than 20 h.