It is a challenge to explore inexpensive noble-metal-free catalysts with long-term stability at low overpotential for water electrolysis to produce hydrogen. Herein, we constructed hierarchical Ni3S2-NiOOH hetero-nano-composite on nickel foam (NF@Ni3S2-NiOOH) through a two-step hydrothermal and electrodeposition method. The as-prepared NF@Ni3S2-NiOOH catalyst was capable of catalyzing hydrogen evolution reaction effectively with a low overpotential of 160 mV at a current density of 10 mA/cm(2) in 1.0 M NaOH, and maintained excellent performance for 45 h without obvious attenuation.