Abstract: Hollow silica microspheres with mesoporous structure were prepared by sol-gel method.In the approach,monodispersed cationic polystyrene microspheres with different size prepared by dispersion polymerization were used as template,dodecylamine as surfactant,the silica shell then coated PS microspheres.At last hexagonal mesoporous and hollow silica microspheres were produced by impregnant and calcination process.TEM and SEM results showed that silica microspheres were monodispersed and hollow;SXRD showed that hexagonal mesopores are in silica microsphere shell;experiment results indicated that the size of silica microspheres can be adjusted by the size of template microspheres,and thickness of the silica shell can be changed by adjusting tetraethyl orthosilicate.Experiment of adsorption load and release to butyl rhodamine B dye confirmed hexagonal mesoporous and hollow silica microspheres have good permeability and sustained release performance. 