Hypersensitive and highly selective nanomaterials for the measurement of heavy metal ions (HMIs) hold a key to electro-analysis. Various works improved the results of analysis but without scientific understanding. Herein, Fe/Mg/Ni-layered double hydroxide (LDH) has been successfully prepared and its electrochemical behavior for Pb(II) detection is also studied using square wave anodic stripping voltammetry (SWASV). The well performance of electrochemistry suggest that the modification with Fe/Mg/Ni-LDH significantly promotes the selectivity and sensitivity toward Pb(II). The sensitivity on Fe/Mg/Ni-LDH modified glassy carbon electrode (GCE) is 68.1 mu A mu M-1 over the range from 0.03 to 1.0 mu M under the optimized conditions. Otherwise, the selectivity, anti-interference, stability measurements and practical implications of Fe/Mg/Ni-LDH modified GCE are also performed. What's more, a reasonable mechanism of detection for Pb(II) including selectivity and sensitivity is proposed based on adsorption and characterized using XPS and XRD. These findings provide a potentially excellent material to improve the sensitivity and selectivity for toxic metal ions as well as a deep understanding of detection. (C) 2017 Elsevier B.V. All rights reserved.