In this article, a novel composite (Mg(OH)2 supported nanoscale zerovalent iron (denoted as nZVI@Mg(OH)2) was prepared and characterized by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy method. The morphology analysis revealed that Mg(OH)2 appeared as self-supported flower-like spheres, and nano Fe0 particles were uniformly immobilized on the surface of their "flower petals", thus aggregation of Fe0 particles was minimized. Then the Pb(II) removal performance was tested by batch experiments. The composite presented exceptional removal capacity (1986.6 mg/g) compared with Mg(OH)2 and nanoscale zerovalent iron due to the synergistic effect. Mechanisms were also explored by a comparative study of the phase, morphology, and surface valence state of composite before and after reaction, indicating that at least three paths are involved in the synergistic removal process: (1) Pb(II) adsorption by Mg(OH)2 (companied with ion exchange reaction); (2) Pb(II) reduction to Pb0 by nanoscale zerovalent iron; and (3) Pb(II) precipitation as Pb(OH)2. The hydroxies provided by Mg(OH)2 can dramatically promote the role of nanoscale zerovalent iron as reducer, thus greatly enhancing the whole Pb(II) sequestration process. The excellent performance shown in our research potentially provides an alternative technique for Pb(II) pollution treatment.