A unique functional electrode made of hierarchal Ni-Mo-S nanosheets with abundant exposed edges anchored on conductive and flexible carbon fiber cloth, referred to as Ni-Mo-S/C, has been developed through a facile biomolecule-assisted hydrothermal method. The incorporation of Ni atoms in Mo-S plays a crucial role in tuning its intrinsic catalytic property by creating substantial defect sites as well as modifying the morphology of Ni-Mo-S network at atomic scale, resulting in an impressive enhancement in the catalytic activity. The Ni-Mo-S/C electrode exhibits a large cathodic current and a low onset potential for hydrogen evolution reaction in neutral electrolyte (pH ~7), for example, current density of 10 mA/cm(2) at a very small overpotential of 200 mV. Furthermore, the Ni-Mo-S/C electrode has excellent electrocatalytic stability over an extended period, much better than those of MoS2/C and Pt plate electrodes. Scanning and transmission electron microscopy, Raman spectroscopy, x-ray diffraction, x-ray photoelectron spectroscopy, and x-ray absorption spectroscopy were used to understand the formation process and electrocatalytic properties of Ni-Mo-S/C. The intuitive comparison test was designed to reveal the superior gas-evolving profile of Ni-Mo-S/C over that of MoS2/C, and a laboratory-scale hydrogen generator was further assembled to demonstrate its potential application in practical appliances.