Aminated polyacrylonitrile fibers (APANFs) were prepared and used as an adsorbent in a series of batch adsorption experiments for the removal of Cr(III) and Cr(VI) species from aqueous solutions of different pH values. The results show that significant amounts of Cr(III) or Cr(VI) species can be adsorbed by the APANFs, although the adsorption performances was greatly dependent upon the solution pH values. In general, the amounts of adsorption for Cr(III) species increased whereas that for Cr(VI) decreased with the increase of the solution pH values, which suggests that different adsorption mechanisms dominated the removal of Cr(III) or Cr(VI) species on the APANFs. X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy revealed that the adsorption of Cr(III) species on the APANFs was largely attributed to the formation of surface complexes between the nitrogen atoms on the APANFs and the Cr(III) species adsorbed, but the adsorption of Cr(VI) species on the APANFs was more likely effected through the formation of hydrogen bonds at high solution pH values or through both electrostatic attraction and surface complexation at low solution pH values. It was found that the Cr(VI)-adsorbed APANFs can be effectively regenerated in a basic solution and be reused almost without any loss of the adsorption capacity, while the Cr(III)-adsorbed APANFs needed to be regenerated in an acidic solution and the regeneration appeared to be less effective.