Benzenesulfonic group containing polyamide-6 (PA6) were fabricated through melting polymerized using epsilon-caprolactam and different proportions of 5-sulphosalicylic acid (5SA). The physicochemical properties of SO3H containing PA6s (SPA6) were determined through FT-IR spectroscopy, TGA and DSC. The morphology of electrospinning fibers of SPA6s were investigated by FE-SEM. Fiber diameters increased with 5SA, and the polymer became un-electrospinnable as 5SA up to 5 wt%. Solution conductivity was a crucial factor for the spinnability of polyelectrolyte. Direction of electric field and material quality of collector could also influence the electrospinning of polyelectrolyte. Sulfonic groups preferred to distribute over the surface of fibers during electrospinnning process comparing to melting spinning, which could render fiber surface more hydrophilic. (C) 2016 Elsevier Ltd. All rights reserved.