Developing low-cost and industrially viable electrode materials for efficient water-splitting performance and constructing intrinsically active materials with abundant active sites is still challenging. In this study, a self-supported porous network Ni(OH)2-CeOx heterostructure layer on a FeOOH-modified Ni-mesh (NiCe/Fe@NM) electrode is successfully prepared by a facile, scalable two-electrode electrodeposition strategy for overall alkaline water splitting. The optimized NiCe0.05/Fe@NM catalyst reaches a current density of 100 mA cm-2 at an overpotential of 163 and 262mV for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively, in 1.0m KOH with excellent stability. Additionally, NiCe0.05/Fe@NM demonstrates exceptional HER performance in alkaline seawater, requiring only 148mV overpotential at 100mA cm-2. Under real water splitting conditions, NiCe0.05/Fe@NM requires only 1.701V to achieve 100mA cm-2 with robust stability over 1000h in an alkaline medium. The remarkable water-splitting performance and stability of the NiCe0.05/Fe@NM catalyst result from a synergistic combination of factors, including well-optimized surface and electronic structures facilitated by an optimal Ce ratio, rapid reaction kinetics, a superhydrophilic/superaerophobic interface, and enhanced intrinsic catalytic activity. This study presents a simple two-electrode electrodeposition method for the scalable production of self-supported electrocatalysts, paving the way for their practical application in industrial water-splitting processes.