Polyacrylonitrile/polypyrrole (PAN/PPy) core-shell structure nanofibers were prepared via electro-spinning followed by in situ polymerization of pyrrole monomer for the removal of hexavalent chromium (Cr(VI)) from aqueous solution. Attenuated total reflections Fourier transform infrared (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS) results confirmed the presence of the polypyrrole (PPy) layer on the surface of PAN nanofibers. The morphology and structure of the core-shell PAN/PPy nanofibers were studied by scanning electron microscopy (SEM) and transmission electron microscope (TEM), and the core-shell structure can be clearly proved from the SEM and TEM images. Adsorption results indicated that the adsorption capacity increased with the initial solution pH decreased. The adsorption equilibrium reached within 30 and 90 min as the initial solution concentration increased from 100 to 200 mg/L, and the process can be described using the pseudo-second-order model. Isotherm data fitted well to the Langmuir isotherm model. Thermodynamic study revealed that the adsorption process is endothermic and spontaneous in nature. Desorption results showed that the adsorption capacity can remain up to 80% after 5 times usage. The adsorption mechanism was also studied by XPS. (C) 2012 Elsevier B.V. All rights reserved.