A novel MoNi₄ electrocatalyst supported by MoO₂ cuboids on nickel foam (MoNi₄/MoO₂@Ni) was developed for efficient hydrogen production in alkaline solutions. This catalyst exhibits a zero onset overpotential, an overpotential of 15 mV at 10 mA cm⁻², and a low Tafel slope of 30 mV per decade in 1M KOH electrolyte, comparable to platinum (Pt) and superior to state-of-the-art Pt-free electrocatalysts. The catalyst's high activity is attributed to its fast water dissociation kinetics, which are facilitated by the controlled diffusion of nickel atoms during synthesis. The MoNi₄ nanoparticles, with a size of 20–100 nm, are formed on the MoO₂ cuboids, leading to a highly active surface for the hydrogen evolution reaction (HER). Density functional theory (DFT) calculations show that the kinetic energy barrier of the Volmer step for MoNi₄ is as low as 0.39 eV, significantly lower than that of Pt. The catalyst demonstrates excellent stability, maintaining its HER activity after 2,000 cyclic voltammetry cycles. The MoNi₄/MoO₂@Ni catalyst was also tested in a water-alkali electrolyser, achieving high current densities (up to 500 mA cm⁻²) at low overpotentials. The study highlights the potential of MoNi₄ as a promising alternative to Pt for hydrogen production in alkaline environments.A novel MoNi₄ electrocatalyst supported by MoO₂ cuboids on nickel foam (MoNi₄/MoO₂@Ni) was developed for efficient hydrogen production in alkaline solutions. This catalyst exhibits a zero onset overpotential, an overpotential of 15 mV at 10 mA cm⁻², and a low Tafel slope of 30 mV per decade in 1M KOH electrolyte, comparable to platinum (Pt) and superior to state-of-the-art Pt-free electrocatalysts. The catalyst's high activity is attributed to its fast water dissociation kinetics, which are facilitated by the controlled diffusion of nickel atoms during synthesis. The MoNi₄ nanoparticles, with a size of 20–100 nm, are formed on the MoO₂ cuboids, leading to a highly active surface for the hydrogen evolution reaction (HER). Density functional theory (DFT) calculations show that the kinetic energy barrier of the Volmer step for MoNi₄ is as low as 0.39 eV, significantly lower than that of Pt. The catalyst demonstrates excellent stability, maintaining its HER activity after 2,000 cyclic voltammetry cycles. The MoNi₄/MoO₂@Ni catalyst was also tested in a water-alkali electrolyser, achieving high current densities (up to 500 mA cm⁻²) at low overpotentials. The study highlights the potential of MoNi₄ as a promising alternative to Pt for hydrogen production in alkaline environments.