AbstractThe construction of efficient and durable multifunctional electrodes for industrial‐scale hydrogen production presents a main challenge. Herein, molybdenum‐modulated phosphorus‐based catalytic electrodes (Mo‐NiP@NF) are prepared via mild electroless plating. Heteroatoms doping or heterostructures construction can reconfigure the intrinsic electronic structure of the pre‐catalyst and optimizes the key intermediates adsorption. Moreover, the (hypo/meta‐)phosphite anions (POxδ−) and molybdate ions (MoOxδ−) on the electrode surface of Mo‐NiP@NF afford resistance to chloride (Cl−) corrosion. Mo‐NiP@NF exhibits ultralow overpotentials of 278/550 and 282/590 mV at 1 A cm−2 during the hydrogen/oxygen evolution reaction (HER/OER) in alkaline simulated and real seawater, respectively, whereas catalytic overall seawater splitting (OWS) reach 1 A cm−2 at 1.96 and 1.97 Vcell. Remarkably, Mo‐NiP@NF maintains stable operation for 1500 h in OWS. The scalability of Mo‐NiP@NF allowing the assembly of proton exchange membrane (PEM) electrolyzer powered by photovoltaic energy, simulating a portable hydrogen‐oxygen respirator provides an oxygen/hydrogen flows of 160/320 mL min−1. Expanding further, the trace ruthenium‐loaded Mo‐NiP@NF catalyst sodium borohydride (NaBH4) hydrolysis achieving a hydrogen generation rate (HGR) of 11049.2 mL min−1 g−1. This work provides strategic innovations and optimization solutions for the economical and mild construction of multi‐scenario durable green energy conversion materials at industrial‐scale application.