Hybrid hollow multi-walled carbon nanotubes (MWCNTs)/polyelectrolytes (PE) nanofibers were prepared by a combination of the electrospinning method and layer-by-layer (LbL) technique. The mixed polystyrene (PS)/MWCNTs nanofibers were obtained by electrospinning method, which were employed as templates to self-assembly multilayered polyelectrolytes by LbL technique. Hollow MWCNTs/PE nanofibers were obtained by selectively removed part of the template: PS, which is confirmed by Raman spectra, transmission electron microscopy (TEM) and scanning electron microscopy (SEM). (C) 2007 Elsevier Ltd. All rights reserved.