Polystyrene (PS) colloidal particles have been used as templates to produce ordered macroporous silica structures. The silica films were deposited from ethanol solution containing acidic water and tetraethyl orthosilicate. The silica-coated PS spheres were characterized using transmission electron microscopy, and the film thickness determined by scanning electron microscopy and calculated from the relative weight of silica remaining after calcination. We found that the thickness of the silica film increased rapidly with time and reached a maximum that varied from 40 to 15 nm at pH 1.5 and 3, respectively. The data could be fitted to a simple first-order equation and the reaction rate and maximum thickness were related to the hydrolysis and condensation rate, respectively. Ordered macroporous structures were formed by centrifuging silica-coated PS spheres. Calcination of the close-packed spheres yielded a continuous silica matrix consisting of a three-dimensional well-ordered network of monodisperse pores