Polymer electrolyte membrane fuel cells (PEMFCs) are one of the most suitable technologies to meet the increasing energy consumption rates. In the early stage, perfluorosulfonic acid-based membranes were commercialized but have many problems such as high production cost, low water management properties and, low tolerance to fuel impurities. To overcome these issues, many studies have been conducted on sulfonated hydrocarbon membranes, but mechanical strength still remains a critical problem. The hydrocarbon-based membranes have a comparatively good ion-exchange capacity and proton conductivity, but decreased mechanical strength, resulting from high water uptake. To solve this, reinforced nanocomposite membranes have been studied. The pore-filling polymerization, one of fabricating methods for the reinforced nanocomposite membranes, was reported in the literature. However, this method is not very satisfactory due to the incompatibility between the substrate and the electrolyte, especially when a commercially available substrate has a fixed porosity and pore size. One strategy to solve such compatibility problem may be fabricating a substrate directly. In other words, the reinforced membrane can be fabricated via simultaneous electrospinning of a substrate and spraying of an electrolyte.In this study, a hydrophobic polysulfone (PSf) was used as a non-conducting substrate to enhance membrane mechanical strength, and a hydrophilic sulfonated poly(arylene ether sulfone) (sPAES) was used as an electrolyte. The properties of the reinforced nanocomposite membranes prepared via the electrospinning and spraying comprising (electrospun PSf/sprayed sPAES) were compared with those of homogeneous (1) (pure) sPAES membrane, (2) electrospun sPAES/sprayed PSf membrane and (3) PSf/sPAES blend membranes. The experimental results revealed that the electrospun PSf/sprayed sPAES membrane-based cell performance was not significantly different from that of the sPAES homogeneous membrane-based cell, but much better than the simple blend membrane-based cell (~ a factor of two). The electrospun PSf/sprayed sPAES membrane exhibited the highest durability according to the US DOE protocol (600 cycles vs. 300 cycles for homogenous sPAES membrane).Based on this study, reinforced nanocomposite membranes with more enhanced performance and durability are expected to be fabricated via optimization of the experimental conditions such as the fiber’s size and pore.