Due to their excellent alkali resistance and chemical stability, polyphenylene sulfide (PPS) fabric membranes are widely used in alkaline water electrolysis (AWE) for hydrogen production. However, traditional PPS membranes suffer from poor hydrophilicity, low airtightness, and high area resistance, resulting in high energy consumption and reduced safety in industrial applications. This study addresses the aforementioned issues by coupling 3‐(2,3‐epoxy propoxy) propyl trimethoxy silane (KH560) via self‐condensation to the PPS membrane and blending it with self‐synthesized yttrium‐stabilized zirconia nanoparticles (YSZNPs). The YSZNPs are loaded onto the modified PPS fiber surface through dip‐coating and hot‐pressing processes, forming a micro‐mechanical interlocking structure that enhances the overall performance of the membrane in practical hydrogen production applications. The findings indicate that the developed composite membrane demonstrate outstanding hydrophilicity, minimal area resistance (0.21 Ω cm2), and elevated bubble point pressure (2.93224 bar). Significantly, tests on gas purity indicate that the produced hydrogen and oxygen attain purities of 99.90% and 99.75%, respectively, when evaluated at a current density of 1.5 A cm−2. Moreover, after 500 h of electrolysis testing in a simulated industrial environment, minimal decline in membrane performance is observed, highlighting the competitive edge of this composite membrane in the current AWE market.