Polystyrene (PS) colloidal particles have been used as templates to produce well-ordered macroporous silica structure. The silica-films on the PS surface were grown from ethanol solution containing acidic water and tetraethyl orthosilicate (TEOS). The films were measured using transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The thickness of the silica film reached a maximum film thickness that varied from 40 to 15 nm, at pH1.5 and pH3. Ordered macro-honeycomb-crystal structures were formed by centrifugation and calcination of silica-coated PS particles. A continuous silica matrix was consisted of a three dimensional well-ordered network like honeycomb.