Electrospun fibers are advanced supporting layers in water purification. Coating the fibers with polydopamine should increase the hydrophilicity and removal efficiency. Here, we report a simple method to fabricate an adsorbent based on polydopamine and electrospun fibers. Polyacrylonitrile and dopamine coelectrospun micro-/nanofibers were selected as supporting layer, and then self-polymerization of polydopamine was used to functionalize the fibers. The polyacrylonitrile/polydopamine micro-/nanofibers were characterized by scanning electron microscopy (SEM), Fourier transform infrared (FTIR) and contact angle. Hexavalent chromium Cr(VI) was then used to investigate the adsorption by fabricated fibers. Results show that the fibers display a super-hydrophilicity and relative excellent adsorption capacityq(m)of 61.65 mg g(-1)of Cr(VI). This finding is explained by the occurrence of amino and hydroxyl groups of polydopamine, and by the porous fibrous morphology of the electrospinning.