Porous matrix immobilization is considered as an effective approach to address the engineering challenges during practical application of nanoadsorbent. In this work, solid and hollow hydrous Zirconium (IV) oxide (ZrO2 center dot nH(2)O, SHZO and HHZO) nanoparticles were enwrapped into millimeter-level beads by polyethersulfone through a mild liquid-liquid phase inversion technique. The beads possess asymmetric and hierarchical structure with an exterior porous surface dense layer and numerous inner interpenetrating finger-like channels, which promote the transportation of molecule and prevent the leaching of nanoadsorbents. As compared to SHZO beads, HHZO beads exhibited higher efficient adsorption capacity toward Pb (II) (104 mg.g(-1)), which could remain at 94% of HHZO nanoparticles. The effects of pH, the stability of adsorbents and coexisting ionic are further explored in detail. The Pb (II) removal mechanism is further studied by the EDS mapping, XPS, FTIR measurements, further indicating the surface hydroxyl groups played a key role in the adsorption process. Fixed-bed column sorption experiment and in situ regeneration were conducted so as to examine the practical application of the beads. Therefore, this kind of beads indicated the potential practical application in industrial wastewater treatment.