The hydrogen evolution reaction (HER) of hydrogen production by water electrolysis under alkaline conditions faces enormous challenges, namely, high catalyst overpotential and reliance on noble metal catalysts. As a transition metal, Ni has the advantages of low cost and excellent HER performance. This study aims to develop high-activity and low-cost HER catalysts to replace noble metal catalysts. In this work, a composite structured HER catalyst based on Ni and hybridized with Ni(OH)2 and NiO was prepared by multi-field coupled electrodeposition. Under the reversible hydrogen electrode (RHE), low overpotentials of 248 mV and 341 mV were achieved at current densities of 500 mA·cm−2 and 1000 mA·cm−2, respectively, making it more suitable for industrial high-current-density water electrolysis for hydrogen production. Moreover, the catalyst achieves long-term stable operation at a high current density of 1000 mA⋅cm−2 in industrial-grade ALK water electrolysis, with highly stable microstructure and chemical composition before and after the durability test. Theoretical calculations show that compared with the NiM catalyst, Ni@NiM enhances the adsorption capacity for water molecules, further optimizes the ion transport of the catalyst, and the complementarity and synergy in the electronic structure among these multiple components significantly improve the HER activity of the catalyst.