An important limitation of polymer electrolyte fuel cell technology is the low mechanical strength and dimensional instability with changes of water content of proton exchange membranes (PEMs). A range of different approaches to more stable PEMs based on Nafion have been studied of which composite materials of Nafion with mechanically stronger polymers is one of the most promising directions. If successful, they will lead to thinner composite PEMs with enhanced fuel cell performance, life span, and cost-effectiveness. Developed in this thesis are electrospinning conditions for the fabrication of electrospun mats for potential application in PEMs. Polysulfone (PSU), poly vinylidene fluoride-co-hexafluoropropylene (PVDF-HFP), and polyvinylidene fluoride (PVDF) were tested as mechanically stronger but inert (minimal contribution to proton transport) polymers that can tolerate the fuel cell condition. PVDF-HFP generated defect free electrospun mats over a wide range of spinning conditions, while PSU required very specific conditions and no successful conditions were found for PVDF mostly due to over-wetting. These mats might function as mechanical support and could be tested as PEMs when filled with Nafion, but the complete filling of electrospun mats with Nafion has been proven difficult. Instead, the electrospinning of Nafion was tested to explore options of electrospinning mixed mats of two different polymers and co-electrospinning of core-sheath fibers. Two commercial Nafion solutions D520 and D2020 with 5 wt% and 20 wt% content of Nafion were electrospun together with polyethylene oxide of two different molecular weights as a carrier polymer. Mats of sufficient quality for PEM tests were obtained with solutions based on 20 wt% content of Nafion, a low flow rate of 0.2 mL/h, and the lower molecular weight polyethylene oxide as the carrier. Finally, coaxial electrospinning conditions for the formation of core-sheath fibers were developed for Nafion as sheath material and PVDF-HFP or PSU as the core material. Defect-free, core-sheath fibers were generated when the concentration of both solutions was high (20 wt%), the Nafion flow rate was about 0.2 mL/h for the sheath, and the core flow rate was below the flow rate of the sheath (0.1-0.15 mL/h for PVDF-HFP and 0.15 mL/h for PSU). Mats of these core-sheath fibers should provide good mechanical strength combined with much better compatibility with Nafion. A straightforward pore filling with Nafion solutions is expected and their investigation as PEMs in fuel cells is planned as future work.