Sunlight-driven electrolytic splitting of water is a promising route to hydrogen production, and widespread implementation has called for the development of inexpensive, robust and large-scale electrodes. Here, nickel nanoparticles partially embedded into carbon fiber cloth (NiΦCFC) is prepared on a large scale (e.g., 40 cm × 40 cm) via a metal-mediated pitting process, which is adopted to fabricate hydrogen evolution reaction electrode for the first time. The partially embedded structure is beneficial for regulating the electron density state of carbon, exposing the nickel catalytic sites and improving the catalytic stability. The two kinds of electrochemical area and density functional theory results confirm that the interface effect between nickel and defective carbon leads into a low Gibbs free energy of H* adsorption. The NiΦCFC as flexible and efficient electrodes require a small overpotential of 131.5 mV to achieve −10 mA cm−2. Note that the two-electrode electrolyzer composed of FeNi layered double hydroxide loaded on CFC (NiFe-LDH/CFC) (+)//NiΦCFC (−) possesses a voltage of 1.54 V at −10 mA cm−2, which can also be powered by a solar cell. The facile and large-scale preparation of NiΦCFC as flexible electrodes could be adapted for the industrial hydrogen production powered by solar energy.