As one of the most important sources for green hydrogen, anion exchange membrane water electrolyzers (AEMWEs) have been developing rapidly in recent decades. Among these components, anion exchange membranes (AEMs) with high ionic conductivity and good stability play an important role in the performance of AEMWEs. In this study, we have developed a simple blending method to fabricate the blended membrane ImPSF-PEGx via the introduction of a hydrophilic PEG into the PSF-based ionic polymer. Given their hydrophilicity and coordination properties, the introduced PEGs are beneficial in assembling the ionic groups to form the ion-conducting channels. Moreover, an asymmetric structure is observed in ImPSF-PEGx membranes with a layer of finger-like cracks at the upper surface because PEGs can act as pore-forming agents. During the study, the ImPSF-PEGx membranes exhibited higher water uptake and ionic conductivity with lower swelling ratios and much better mechanical properties in comparison to the pristine ImPSF membrane. The ImPSF-PEG1000 membrane showed the best overall performance among the membranes with higher ionic conductivity (82.6 mS cm−1 at 80 °C), which was approximately two times higher than the conductivity of ImPSF, and demonstrated better mechanical and alkaline stability. The alkaline water electrolyzer assembled by ImPSF-PEG1000 achieved a current density of 606 mA cm−2 at 80 °C under conditions of 1 M KOH and 2.06 V, and maintained an essentially unchanged performance after 48 h running.