A novel three-dimensional nanoporous tungsten disulfide/acetylene black (nanoporous-WS₂/AB) electrocatalyst was successfully prepared by template assisted hydrothermal method and further applied to hydrogen evolution reaction (HER) for the first time. Surface morphology and crystalline structure of as-prepared nanoporous-WS₂/AB were characterized by scanning electron microscopy and X-ray diffractometer. The electrocatalytic properties of as-prepared materials modified electrodes for HER were investigated by polarization curves, electrochemical impedance spectroscopy and Tafel polarization curves in 0.50 M H₂SO₄ solution. Compared with WS₂, AB and WS₂/AB based electrodes, nanoporous-WS₂/AB based electrode exhibited a much higher electrocatalytic activity which was attributed to the synergistic effect between nanoflower WS₂ and amorphous AB, as well as the presences of dual templates of amorphous AB and porous 4A-zeolite. The exchange current density of nanoporous-WS₂/AB electrode was 1.6 and 2.5 times larger than that of WS₂/AB and pure WS₂ based electrode at -400 mV, respectively. The results indicated that nanoporous-WS₂/AB composite would be a promising candidate for the potential application in HER.