Polystyrene resins (PS) have been practical ion exchangers for radionuclides removal from water. However, nonspecific effects of ion exchange groups continue to be a major obstacle for emergency treatment with coexisting ions of high concentrations. The selectivity for Cs + enables zirconium phosphate (ZrP) to be the most promising inorganic sorbent for radioactive cesium extraction, despite being difficult to synthesize and causing excessive pressure loss in fixed-bed reactors due to fine powder. Herein, through facile confined crystallization in host macropores, we prepared PS confined alpha-ZrP nanocrystalline (ZrP-PS). Size-screen sorption of layered alpha-ZrP and sulfonic acid group preconcentration of PS synergistically enable a considerably higher Cs + affinity of ZrP-PS than PS, as confirmed by X-ray photoelectron spectroscopy (XPS) analysis. ZrP-PS demonstrated remarkable cesium sequestration performance in both batch and continuous experiments, with a high adsorption capacity of 269.58 mg/g, a rapid equilibrium within 80 min, and a continuous effluent volume of 2300 L/kg sorbents. Given the excellent selectivity for Cs + and flexibility to separate from treated water, ZrP-PS holds great promise as purification packages for the emergency treatment of radioactively contaminated water. (c) 2023 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.