Hollow sphere silica (HSS) materials have been extensively studied such as drug delivery system, catalyst, and display because of their extraordinary structure. Nano-sized HSS materials were synthesized by sol-gel method applying cationic surfactant CTACl in basic condition and nonionic surfactant pluronic F-68 in acidic condition, respectively. HSS samples were characterized by TEM and N2-sorption. Diameter of HSS-CT, which was prepared by CTACl, is about 250 nm and surface area is about 1,000 m2/g, but diameter of HSS-P, which was prepared by F-68, is about 30 nm and surface area is about 500 m2/g.