Electrospinning is a relatively simple method to produce submicron fibers from solutions of different polymers and polymer blends. In this work, the interior structure of electrospinning PAN nanofibers by adding different content of LiCl is investigated. The diameter of nanofibers, electrospun by solutions with different content of LiCl reduces in the following order: 1 wt.%LiCl>2 wt.%LiCl>3 wt.%LiCl>4 wt.%LiCl. The X-ray diffraction patterns of electrospinning nanofibers with or without LiCl do not change much. The crystallinity of nanofibers with LiCl is generally lower than that of nanofibers without LiCl. Moreover, the added salts are propitious to electrospinning and the chemical composition of PAN is also found to be unchanged. (C) 2007 Elsevier B.V. All rights reserved.