Functionalized hollow siliceous spheres (HSSs) have been prepared by surface modification with trimethylchlorosilane (TMCS) for the removal of volatile organic compounds (VOCs). The resultant HSSs-TMCS possesses a uniform and well-dispersed hollow spherical structure, high surface area, large total pore volume, high VOCs adsorption capacity, and small water vapor adsorption capacity. The adsorption and desorption performance of HSSs-TMCS under static (n-hexane and 93# gasoline) and dynamic (n-hexane) conditions was investigated. Compared with commercial silica gel (SG) and activated carbon (AC), HSSs-TMCS show higher capacity of adsorbing n-hexane and 93# gasoline with good stability and low water vapor adsorption capacity under static adsorption conditions, higher dynamic adsorption capacity and stable breakthrough time under dynamic adsorption conditions. The high efficiency and stability of functionalized HSSs are associated with their unique hollow morphology and structure parameters. The designed HSSs-TMCS with high VOCs removal capacity and recyclability are promising candidates for the treatment of air pollution. (C) 2014 Elsevier B.V. All rights reserved.