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Seawater splitting represents an inexpensive and attractive route for producing hydrogen, which does not require a desalination process. Highly active and durable electrocatalysts are required to sustain seawater splitting. Herein we report the phosphidation-based synthesis of a cobalt–iron–phosphate ((Co,Fe)PO₄) electrocatalyst for hydrogen evolution reaction (HER) toward alkaline seawater splitting. (Co,Fe)PO₄ demonstrates high HER activity and durability in alkaline natural seawater (1 M KOH + seawater), delivering a current density of 10 mA/cm² at an overpotential of 137 mV. Furthermore, the measured potential of the electrocatalyst ((Co,Fe)PO₄) at a constant current density of −100 mA/cm² remains very stable without noticeable degradation for 72 h during the continuous operation in alkaline natural seawater, demonstrating its suitability for seawater applications. Furthermore, an alkaline seawater electrolyzer employing the non-precious-metal catalysts demonstrates better performance (1.625 V at 10 mA/cm²) than one employing precious metal ones (1.653 V at 10 mA/cm²). The non-precious-metal-based alkaline seawater electrolyzer exhibits a high solar-to-hydrogen (STH) efficiency (12.8%) in a commercial silicon solar cell.