In this study, multilayered NiMo/CoMn/Ni cathodic electrodes were prepared by the multilayered electrodeposition method. The multilayered structure includes a nickel screen substrate, CoMn nanoparticles at the bottom, and cauliflower-like NiMo nanoparticles at the top. The multilayered electrodes have a lower overpotential, preferable stability, and better electrocatalytic performance than monolayer electrodes. In a three-electrode system, the overpotentials of the multilayered NiMo/CoMn/Ni cathodic electrodes at 10 and 500 mA/cm 2 are only 28.7 and 259.1 mV, respectively. The overpotential rise rate of the electrodes after constant current tests at 200 and 500 mA/cm 2 was 4.42 and 8.74 mV/h, respectively, and the overpotential rise rate after 1000 cycles of cyclic voltammetry of the electrodes was 1.9 mV/h, while the overpotential rise rate after the three stability tests of the nickel screen was 5.49, 11.42, and 5.1 mV/h. According to the Tafel extrapolation polarization curve, the E corr and I corr of the electrodes were -0.3267 V and 1.954 × 10 -5 A/cm 2 , respectively. The charge transfer rate of the electrodes is slightly slower than that of the monolayer electrodes, indicating that its corrosion resistance is more excellent. An electrolytic cell was designed for the overall water-splitting test, and the current density of the electrodes was 121.6 mA/cm 2 at 1.8 V. In addition, the stability of the electrodes is excellent after intermittent testing for 50 h, which can greatly reduce power consumption and is more suitable for industrial overall water-splitting tests. In addition, the three-dimensional model was used to simulate the three-electrode system and alkaline water electrolytic cell system, and the simulation results are consistent with the experimental results. The hydrogen adsorption free energy (Δ G H ) of the electrodes was -1.0191 eV, which was evaluated by density functional theory (DFT). The Δ G H is closer to zero than that of the monolayer electrodes, indicating that the surface has stronger adsorption of hydrogen atoms.