A novel amorphous nanoporous PdCuNi-S electrocatalyst is synthesized by a two-step dealloying method. The as-formed nanoporous PdCuNi-S catalyst exhibits excellent catalytic activity for the hydrogen evolution reaction (HER) in acidic media, which is very close to commercial Pt/C catalyst. The overpotential at 10 mA cm(-2) and Tafel slope are 48 mV and 35 mV dec(-1), respectively. In addition, the catalyst shows good electrochemical stability in HER. The outstanding property of PdCuNi-S catalyst for hydrogen generation is attributed to the bicontinuous nanoporous structure, improved charge transfer, more bridging S-2(2-) and/or apical S2- in amorphous state and synergetic interactions of Pd, Cu, Ni and S.