Using a sol-gel processing and electrospinning technique, extrathin fibers of PVA (polyvinyl alcohol)/lithium chloride/cobalt acetate composite were prepared. After calcinations of the above precursor fibers at 600 degrees C, LiCoO2 nanofibers with a diameter of 100-150 nm, were successfully obtained. Measurements of TG/DTA, IR, XRD, Raman, SEM, EDS, respectively, were performed to characterize the properties of the as-prepared materials. We observed a strong correlation between crystalline phase and morphology of the fibers and calcinations temperature. (c) 2006 Elsevier Ltd. All rights reserved.