An attempt was made to prepare hollow silica microspheres by an oil-in-water emulsion which proposed to use waste polystyrene organic solution as oil phase. Effects of the kinds and amounts of surfactants and the concentration of waste polystyrene solution on the nanosized hollow silica microspheres were studied. The prepared hollow silica microspheres were characterized by TEM, XRD, TG-DTA and particle size distribution analyzer. The experimental results showed that the waste polystyrene organic solution was successfully treated as oil core and the cores could be removed at about 350°C. Meanwhile, the obtained hollow microspheres were amorphous with an average particle size of 40nm. The hollow silica microspheres could be obtained with the selected surfactant.