Polyacrylonitrile/polypyrrole (PAN/PPy) core/shell nanofiber mat was prepared through electrospinning followed by a simple chemical oxidation method. The polypyrrole-functionalized nanofiber mats showed selective adsorption performance for anions. The interaction between heavy metal anions and polypyrrole (especially the interaction between Cr2O72- and polypyrrole) during the adsorption process was studied. The results showed that the adsorption process included two steps: one was the anion exchange process between the Cl- and Cr(VI), and the other was the redox process for the Cr(VI) ions. The adsorption amount was related to the protonation time of the PAN/PPy nanofiber mat and increased as protonation time increased. Meanwhile, the Cr(VI) ions were reduced to Cr(III) through the reaction with amino groups of polypyrrole (from secondary amines to tertiary amines). PAN/PPy nanofiber mat showed high selectivity for Cr(VI), and the adsorption performance was nearly unaffected by other co-existing anions (Cl-, NO3-, and SO42-) except for PO43- for the pH change. (C) 2014 Elsevier B.V. All rights reserved.