Mesoporous organic-inorganic hybrid siliceous hollow spheres (MOSs) were successfully synthesized by co-condensation of tetraethylorthosilicate (TEOS) and 1, 2-bis(triethoxysilyl)ethane (BTSE) with reverse micelle as template under basic condition. Structure and property of the prepared samples were characterized by different methods. The MOSs was used for VOCs removal with commercial silica gel (SG) and activated carbon (AC) as references. It is found that the sample with initial BTSE/(BTSE+TEOS) molar ratio of 10% (MOS-10%) displays uniform hollow mesostructure with the highest static VOCs adsorption capacities (1.28 g·g^-1 n-hexane, 1.25 g·g^-1 toluene and 1.14 g·g^-1 92# gasoline), and the lowest water vapor adsorption capacity of 0.630 g·g^-1. Dynamic single component (n-hexane, toluene adsorption under dry condition or n-hexane adsorption under high humidity condition, 95% RH) adsorption results show that MOS-10% has the best breakthrough times, adsorption capacities, and hydrophobicity. For binary component (n-hexane and toluene) adsorption, MOS-10% preferred to adsorb n-hexane rather than adsorb toluene. The higher dynamic VOCs capacity of MOS is attributed to the cooperation of the introduced organic groups, surface area and pore volume. The MOSs with high VOCs removal capacity and excellent recyclability show great potential for VOCs adsorption.