The hexadecyltrimethylammonium bromide (HDTMAB) immobilized hollow mesoporous silica spheres were prepared for the efficient removal of perfluorooctane sulfonate (PFOS) from aqueous solution. Besides the traditional sorption behavior including sorption kinetics as well as effect of solution pH and temperature, the effect of increasing volume which simulated the natural river where the rate of solute and solvent was relatively constant and solution volume was always changing was investigated. The result indicated that the residual PFOS concentrations in aqueous phase decreased with increasing solution pH and ionic strength, whereas they increased with increasing temperature. The HDTMAB immobilized material still maintained high efficiency after increasing volume, that is, the removal kept more than 99% after the treatment when the initial PFOS concentration was 1 mg L(-1). The uptake behavior and morphology of spheres which was characterized by transmission electron microscopy (TEM) revealed that the additional HDTMAB and mesoporous shell were responsible for the enhanced sorption of PFOS. It was concluded that electrostatic interaction and Ca-bridge role played an important role in the sorption of PFOS on the mesoporous SiO(2) hollow spheres, whereas, hydrophobic interaction contributed to the nice sorption performance of PFOS on the HDTMAB immobilized sorbent.