AbstractBifunctional electrocatalysts with excellent activity and durability are highly desirable for alkaline overall water splitting, yet remain a significant challenge. In this contribution, palm‐like Mo5N6/Ni3S2 heterojunction arrays anchored in conductive Ni foam (denoted as Mo5N6‐Ni3S2 HNPs/NF) are developed. Benefiting from the optimized electronic structure configuration, hierarchical branched structure and abundant heterogeneous interfaces, the as‐synthesized Mo5N6‐Ni3S2 HNPs/NF electrode exhibits remarkably stable bifunctional electrocatalytic activity in 1 m KOH solution. It only requires ultralow overpotentials of 59 and 190 mV to deliver a current density of 10 mA cm−2 for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in 1 m KOH solution, respectively. Importantly, the overall water splitting electrolyzer assembled by Mo5N6‐Ni3S2 HNPs/NF exhibits an exceptionally low cell voltage (1.48 V@10 mA cm−2) and outstanding durability, surpassing most of the reported Ni‐based bifunctional materials. Density functional theory (DFT) further confirms the heterostructure can optimize the Gibbs free energies of H and O‐containing intermediates (OH, O, OOH) during HER and OER processes, thereby accelerating the catalytic kinetics of electrochemical water splitting. The findings provide a new design strategy toward low‐cost and excellent catalysts for overall water splitting.