Polyacrylonitrile/polyaniline core/shell nanofibers were prepared via electrospinning followed by in situ polymerization of aniline. Nanofibers with different morphology were obtained by changing the polymerization temperature. When used as absorbent for Cr(vi) ions, the core/shell nanofiber mats exhibit excellent adsorption capability. The equilibrium capacity is 24.96, 37.24, and 52.00 mg g-1 for 105, 156, and 207 mg L-1 initial Cr(vi) solution, respectively, and the adsorption capacity increases with temperature. The adsorption follows a pseudo second order kinetics model and is best fit using the Langmuir isotherm model. The mats show excellent selectivity towards Cr(vi) ions in the presence of competing ions albeit a small decrease in adsorption is observed. The mats can be regenerated and reused after treatment with NaOH making them promising candidates as practical adsorbents for Cr(vi) removal. © The Royal Society of Chemistry 2013.