A chiral tungstic ionic liquid was prepared with 1,12-dibromododecane, S-nicotine and sodium tungstate. Sodium silicate was taken as silicon source. And then functionalized hollow mesoporous silica spheres were prepared by a one-step hydrothermal method. They were characterized by SEM, TEM, FTIR, UV-Vis, N2 adsorption-desorption, XPS, ICP-OES, contact angles, electronic circular dichroism(ECD), etc. and their catalytic performance was investigated by the dihydroxylation of olefins. The results showed that the diameter of the hollow mesoporous silica sphere is about 100 nm, the BET surface area is 20-53 m2/g, and the average pore diameter is 7.7-16 nm. The chiral tungstic ionic liquid was successfully embedded in the mesoporous hollow sphere. The spherical solids presented the circular dichroism. The catalyst with n(W)∶n(Si)=0.25∶0.75 performed best during the olefin dihydroxylation reaction, with yield of (R)-phenylethylene glycol of 89.6% and even up to 87% after being recycled for 5 times. Since the contrast sample without tungsten was observed as amorphous nanoparticles, it can be speculated that the tungstic-based ionic liquid displayed a structure-directing effect on the formation of mesoporous hollow spheres.