Electrospun polyacrylonitrile (PAN) copolymer nanofibers with diameters of similar to 0.3 mu m were prepared as highly aligned bundles. The as-electrospun nanofiber bundles were then stretched in steam at similar to 100 degrees C into 2, 3, and 4 times of the original lengths. Subsequently, characterizations and evaluations were carried out to understand morphological, structural, and mechanical properties using SEM, 2D WAXD, polarized FT-IR, DSC, and mechanical tester; and the results were compared to those of conventional PAN copolymer microfibers. The study revealed that: (1) the macromolecules in as-electrospun nanofibers were loosely oriented along fiber axes; although such an orientation was not high, a small extent of stretching could effectively improve the orientation and increase the crystallinity; (2) most of macromolecules in the crystalline phase of as-electrospun and stretched nanofibers possessed the zig-zag conformation instead of the helical conformation; and (3) the post-spinning stretching process could substantially improve mechanical properties of the nanofiber bundles. To the best of our knowledge, this study represented the first successful attempt to stretch electrospun nanofibers; and we envisioned that the highly aligned and stretched electrospun PAN copolymer nanofibers could be an innovative type of precursor for the development of continuous nano-scale carbon fibers with superior mechanical strength. (C) 2010 Elsevier Ltd. All rights reserved.