Activated carbon fiber (ACF) webs with a non-woven multi-scale texture were fabricated from polyacrylonitrile (PAN), and their electrosorption performance in capacitive deionization for desalination was investigated. PAN nanofibers were prepared by electrospinning, followed by oxidative stabilization and activation with carbon dioxide at 750-900 degrees C, resulting in the ACF webs that were characterized by Xray diffraction, Raman spectroscopy, scanning electron microscopy and nitrogen adsorption. The results show that the as-made ACFs have a specific surface area of 335-712 m(2)/g and an average nanofiber diameter of 285-800 nm, which can be tuned by varying the activation temperature. With the ACF webs as an electrode, an electrosorption capacity as high as 4.64 mg/g was achieved on a batch-type electrosorptive setup operated at 1.6 V. The ACF webs made by electrospinning are of potential as an excellent electrode material for capacitive deionization for desalination. (C) 2012 Elsevier Ltd. All rights reserved.