A self-supported silver electrode was prepared by plasma spraying and used for catalysing the hydrogen evolution reaction. Thanks to the non-equilibrium synthetic conditions, the silver catalyst exposes high-energy (200) crystal planes, which enhance the adsorption of hydrogen and improve the intrinsic catalytic activity. As a result, the silver catalyst delivers an overpotential of 349 mV at 10 mA cm −2 , which was much lower than those of Ag foil (742 mV) and commercial Ag powder (657 mV). This work provides a new idea of preparing active electrocatalysts by traditional processes. A physical technique, plasma spraying, was adopted to grow a self-supported silver electrode with a high-energy (200) surface, which improves the intrinsic activity for the hydrogen evolution reaction.