Developing composite separator membranes with low area resistance, high bubble point pressure, and long-term safety and stability is crucial for alkaline water electrolysis for hydrogen production as a key component of electrolyzer systems. In this study, PPS mesh fabric reinforced PSF@ZrO2 composite separator membranes were successfully prepared using the immersion-drawing phase inversion method, with PSF as the alkali-resistant polymer matrix and porous irregular ZrO2 nanoparticles as the hydrophilic additive. The experimental results showed that replacing commercial ZrO2 with porous irregular ZrO2 nanoparticles at an 85 wt% ZrO2 nanoparticle loading improved both bubble point pressure and current transmission efficiency, attributed to the change in the morphological structure of the ZrO2 nanoparticles. The P-Z85 composite separator membrane exhibited highly promising characteristics, with a high bubble point pressure of 3.76 bar and a low area resistance of 0.20 Ω cm2. Stability tests conducted in 30 wt% KOH electrolyte at 80 °C and a current density of 0.65 A cm−2 demonstrated excellent continuous electrolysis stability for the P-Z85 composite separator membrane. These results indicate that the PSF@ZrO2/PPS composite separator membrane prepared in this study exhibits excellent performance in 30 wt% KOH electrolyte, significantly extending its service life.