Nanofibers of highly sulfonated (IEC similar to 4.5 meq/g) polystyrene (SPS) were successfully electrospun. To accomplish this, the process of electrospinning this difficult-to-spin material was studied in detail. Fiber quality was optimized by manipulating the process and solution variables to fabricate continuous bead-free fibers. Bead-free fibers (average diameter 260 nm) were electrospun from 25 wt% SPS (500 kDa) in DMF at an electrode separation of 10 cm, an applied voltage of 16.5 kV and a flow rate of 0.3 mL/h. With increasing solution concentration, and thereby the solution viscosity, the morphology changed from beads to bead-on-string fibers to continuous cylindrical fibers. Beaded fibers and continuous bead-free fibers of SPS (500 kDa) could be spun at similar to 2 C-e and 3.5 C-e, respectively, where C-e is the entanglement concentration determined from solution-viscosity measurements. The onset of formation of beaded fibers coincided with a sharp transition in the scaling of the storage modulus-concentration relationship. (C) 2010 Elsevier Ltd. All rights reserved.