In this paper, we fabricated hollow multilayered polyelectrolyte nanofibers by the combination of the layer-by-layer (LBL) method and electrospinning technique, the hollow nanofibers with an inner hollow diameter about 400-500 nm was obtained while the shell is about 100 nm. The relationship between the morphologies of the obtained dried hollow multilayered fibers and the deposited polyelectrolyte layer numbers was studied. Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy (FTIR) were employed to study the obtained hollow multilayered polyelectrolyte nanofibers. Organic/inorganic complex fiber also can be obtained by this method. (c) 2006 Elsevier B.V. All rights reserved.