The primary goal of this study is to develop a novel PEMs with unique surface structure utilizing the high viscosity of the impregnation solution. SiO2 nanofiber mats were prepared via the electrospinning method and introduced into sulfonated poly(ether sulfone) (SPES) matrix to prepare hybrid membrane. The effect of concentration of impregnation solution on the morphology and properties of the proton exchange membranes (PEMs), including thermal stability, water uptake, dimensional stability, proton conductivity, and methanol permeability were investigated. SEM results showed that a unique surface structure was prepared due to the high solution concentration. Moreover, the hydrophilic nanofibers on the surface constructed continuous proton pathways, which can enhance the proton conductivity of the membranes, a maximum proton conductivity of 0.125 S/cm was obtained when the SPES concentration was 40 wt% at 80 A degrees C, and the conductivity was improved about 1.95 times compared to that of pure SPES membrane. The SiO2 nanofiber mat-supported hybrid membrane could be used as PEMs for fuel cell applications.