Micrometer-sized hollow silica particles were synthesized by sol-gel reaction in water-in-oil emulsion. To obtain hollow structures in silica particles, the viscosity of water droplets in W/O emulsion was controlled with polyethylene glycol (PEG) or polyvinylpyrrolidone (PVP). To stabilize the emulsion structure, hydroxypropyl cellulose (HPC) was added to the oil phase. Without HPC, the particles have an irregular shape and hardly have a particulate form. As the concentration of HPC increased from 0.8 to 1.4 wt%, the size of silica particles decreased from 10 to I mum. But above 1.4 wt%, the solution was very viscous, so that it was difficult to handle. Especially, the role of PEG or PVP in the water phase was very important, not only because it stabilized the W/O emulsion structure, but also because it influenced the formation of hollow structure. Interestingly, the hollow silica particles were formed when the molar ratio of water to TEOS (Rw) was 4 and the concentrations of PEG and HPC were 6 and 1.4 wt%, respectively. Also, when PEG was replaced with polyvinylpyrrolidone (PVP), hollow silica particles ranging from 3 to 7 mum were formed. (C) 2003 Elsevier Inc. All rights reserved.