Currently, platinum-based electrocatalysts show the best performance for hydrogen evolution. All hydrogen evolution reaction catalysts should however obey Sabatier's principle, that is, the adsorption energy of hydrogen to the catalyst surface should be neither too high nor too low to balance between hydrogen adsorption and desorption. To overcome the limitation of this principle, here we choose a composite (rhodium/silicon nanowire) catalyst, in which hydrogen adsorption occurs on rhodium with a large adsorption energy while hydrogen evolution occurs on silicon with a small adsorption energy. We show that the composite is stable with better hydrogen evolution activity than rhodium nanoparticles and even exceeding those of commercial platinum/carbon at high overpotentials. The results reveal that silicon plays a key role in the electrocatalysis. This work may thus open the door for the design and fabrication of electrocatalysts for high-efficiency electric energy to hydrogen energy conversion.