AbstractThe effect of the side‐chain length (short side chain and long side chain, SSC and LSC, respectively) of perfluorosulfonic acid (PFSA) ionomers on the properties of nanofibers obtained by electrospinning ionomer dispersions in high dielectric constant liquids has been investigated with a view to obtaining electrospun webs as components of fuel cell membranes. Ranges of experimental conditions for electrospinning LSC and SSC PFSAs have been explored, with a scoping of solvents, carrier polymer and PFSA ionomer concentrations, and carrier polymer molecular weight. Under optimal conditions, the electrospun mats derived from SSC and from LSC PFSA show distinct fiber dimensions that arise from the different chain lengths of the respective ionomers. Enhanced interchain interactions in SSC PFSA with low equivalent weight compared to LSC PFSA result in a considerably lower average fiber diameter and a markedly narrower fiber size distribution. The proton conductivity of nanofiber mats of SSC and LSC PFSA with equivalent weights of 830 and 900 g mol−1, respectively, are 102 and 58 mS cm−1 at 80°C and 95% relative humidity. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013