ZnS hollow nanospheres with nanoporous shell were successfully synthesized through the evolvement of ZnO nanospheres which were synthesized by hydrothermal method with poly (sodium-p-styrene sulfonate) (PSS) as surfactant at low temperature. The as-synthesized samples were characterized with X-ray diffraction (XRD), transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), UV/vis spectrum and N 2 adsorption. The results showed that the shell of as-synthesized ZnS hollow structure was composed of many fine crystallites and had a nanoporous structure with pore diameter about 4nm demonstrated by N 2 adsorption/desorption isotherm. The sample possessed efficiency of photocatalytic degradation on X-containing (X=Cl, Br, I) organic pollutants.