In the present study, the formation of high aspect ratio nanofibers in polyamide-6 was investigated as a function of applied voltage ranging from 15 to 25 kV using electrospinning technique. All other experimental parameters were kept constant. The electrospun polyamide-6 nanofibers were characterized by field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF). FE-SEM images of polyamide-6 nanofibers showed that the diameter of the electrospun fiber was decreased with increasing applied voltage. At the critical applied voltage, the polymer solution was completely ionized to form the dense high aspect ratio nanofibers in between the main nanofibers. The diameter of the polyamide-6 nanofibers was observed to be in the range of 75-110 nm, whereas the high aspect ratio structures consisted of regularly distributed very fine nanofibers with diameters of about 9-28 nm. Trends in fiber diameter and diameter distribution were discussed for the high aspect ratio nanofibers. TEM results revealed that the formation of double layers in polyamide-6 nanofibers and then split-up into ultrafine fibers. The electrically induced double layer in combination with the polyelectrolytic nature of solution is proposed as the suitable mechanisms for the formation of high aspect ratio nanofibers in polyamide-6. (C) 2010 Elsevier B. V. All rights reserved.