AbstractDeveloping transition metal based overall water splitting (OWS) electrocatalysts with high efficiency, low‐cost, large current density, and long‐term stability is crucial for industrial electrolysis of water, but remains a major challenge. In this study, a hierarchical electrocatalyst with MoS2/Ni3S2 heterojunctions and a tiny amount of Au nanoparticles grown on nickel foam (MoS2/Ni3S2‐Au@NF) has been developed by a one‐step hydrothermal method. The heterojunctions and Au nanoparticle decoration induce the electron‐rich interfaces in the catalyst, which facilitate the synergistic adsorption of both OER and HER intermediates. As a result, MoS2/Ni3S2‐Au@NF possesses an excellent bifunctional electrocatalytic performance in 1 M KOH with low HER overpotential (78 mV@10 mA cm−2, 253 mV@500 mA cm−2), low OER overpotential (261 mV@50 mA cm−2, 435 mV@500 mA cm−2), and outstanding cyclical stability and continuous stability, which are superior than typical benchmarks of Pt/C and RuO2. An electrolyzer assembled with the self‐supported MoS2/Ni3S2‐Au@NF electrode also displays excellent OWS activity and stability with a current density beyond 100 mA cm−2. This experiment is responding a potential alternative non‐precious metal electrocatalyst for OWS at industrial settings, and thus promotes the real‐world application of hydrogen energy conversions.