Electrolysis of water to generate hydrogen fuel is an attractive renewable energy storage technology. However, grid-scale freshwater electrolysis would put a heavy strain on vital water resources. Developing cheap electrocatalysts and electrodes that can sustain seawater splitting without chloride corrosion could address the water scarcity issue. Here we present a multilayer anode consisting of a nickel–iron hydroxide (NiFe) electrocatalyst layer uniformly coated on a nickel sulfide (NiSx) layer formed on porous Ni foam (NiFe/NiSx-Ni), affording superior catalytic activity and corrosion resistance in solar-driven alkaline seawater electrolysis operating at industrially required current densities (0.4 to 1 A/cm²) over 1,000 h. A continuous, highly oxygen evolution reaction-active NiFe electrocatalyst layer drawing anodic currents toward water oxidation and an in situ-generated polyatomic sulfate and carbonate-rich passivating layers formed in the anode are responsible for chloride repelling and superior corrosion resistance of the salty-water-splitting anode. Significance Electrolysis of water to generate hydrogen fuel could be vital to the future renewable energy landscape. Electrodes that can sustain seawater splitting without chloride corrosion could address the issue of freshwater scarcity on Earth. Herein, a hierarchical anode consisting of a nickel–iron hydroxide electrocatalyst layer uniformly coated on a sulfide layer formed on Ni substrate was developed, affording superior catalytic activity and corrosion resistance in seawater electrolysis. In situ-generated polyanion-rich passivating layers formed in the anode are responsible for chloride repelling and high corrosion resistance, leading to new directions for designing and fabricating highly sustained seawater-splitting electrodes and providing an opportunity to use the vast seawater on Earth as an energy carrier.