Adsorption is recognized as one of the most promising technologies applied to remove heavy metals from contaminated water. However, the adsorption efficiency often decreases because of the aggregation and loss of adsorbents. Herein, a novel adsorbent was synthesized by intercalation ethylenediaminetetraacetic acid (EDTA) into layered double hydroxides (LDH) and subsequent encapsulated into PAN polymer matrix using electrospinning. The synthesized electrospun nanofiber membrane (MgAl-EDTA-LDH@PAN) was found to combine the advantages of LDH@PAN nanofiber membrane (high surface area, easy to separate, free from aggregation and loss) and EDTA (powerful chelating agent). The adsorption performance of the MgAl-EDTA-LDH@PAN was evaluated using Cu(II) as target metals by varying experimental conditions such as pH, contact time, initial adsorbent dosage, and temperature. The maximum adsorption capacity of MgAl-EDTA-LDH@PAN was 120.77 mg/g with the initial Cu(II) concentrations ranging from 0.6 to 40 mg/L. MgAl-EDTA-LDH@PAN was also used in real industrial contaminated water treatment, and the final effluent was approximate to class-I criteria of the National Wastewater Discharge Standard of China. (GB 8978-1996). In addition, Cu K-edge XAS and XPS analyses were applied for unraveling the adsorptive performance of MgAl-EDTA-LDH@PAN by revealing the molecular-level mechanism of Cu(II) uptake. (C) 2017 Elsevier B.V. All rights reserved.