In the present work, the pure polyamide6 (PA6) nanofier and PA6/organically modified montmorillonite (O-MMT) composite nanofiber were firstly prepared by a facile compounding process with electrospinning, and then coated by nanosize Fe2O3 using magnetron sputter technique. The effects of Fe2O3 sputter coating on structures, surface morphology and thermal stability were characterized by scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDX), atomic force microscope (AFM) and thermogravimetric analyses (TGA), respectively. The SEM images showed that the diameters of composite nanofiber were decreased with the loadings of O-MMT and the nanosize Fe2O3 is well coated on the surface of the homogeneous and cylindrical nanofibers. The XPS spectra reflected the chemical features of the deposited nanostructures. The EDX confirmed the presence of the O-MMT and Fe2O3 in the fibers. The AFM observation revealed that there was a remarkable difference in the surface morphology of composite nanofiber before and after sputter coating. The TGA analysis indicated the barrier effects of silicate clay layers and catalysis effects of Fe2O3 improved thermal stability properties of the composite nanofiber. (C) 2008 Elsevier B.V. All rights reserved.