An environmentally benign and efficient hydrothermal carbonization method is widely applied for the preparation of carbon-based adsorbents. However, the adsorption capacity toward anionic species would be influenced due to the negatively charged surface of the traditional hydrothermal carbonaceous materials; moreover most of the carbonaceous materials were in the form of powder which restricted the practical applications. Herein, amino-rich hydrothermal carbon-coated electrospun polyacrylonitrile fiber (PAN@NC) adsorbents were obtained through one-step hydrothermal carbonization approach assisted by diethylenetriamine using polyacrylonitrile (PAN) fibers as the templates, which showed highly efficient adsorption for anionic pollutants. The PAN@NC fibers were characterized in detail to confirm their structures and composition. The flexible and robust PAN@NC fiber membrane exhibited high adsorption capacity and good regeneration and recycling ability toward the anionic metal ion Cr(VI) and herbicide 2,4-dichlorophenoxyacetic acid (2,4-D). According to the Langmuir model, the adsorption behaviors showed monolayer adsorption capacities of 290.70 mg/g and 164.47 mg/g for Cr(VI) and 2,4-D, respectively, which were higher than that of many other adsorbents. Recycling study indicated that the removal efficiencies for both pollutants retained above 90% after five cycles. These findings demonstrate that PAN@NC fibers are promising adsorbents for the removal of anionic pollutants from wastewater solutions. (C) 2016 Elsevier Inc. All rights reserved.