A method for preparing 3D ordered macroporous silicate materials was developed by using the ordered stacking structure of monodispersed polystyrene latex as a template. By using a modified sol|gel procedure, the ordered template was permeated and filled with silicate, and the title porous materials was formed after removing the template by calcination at high temperature. Moreover, the pores were highly ordered throughout all the sample. After observing the morphological profile of the sample before calcination, it was found that silicate existed in two typical morphologies: monodispersed particles in the cavities and interconnected network within the interstice of the template. The transition morphology was rod|like formed by the condensation of the silicate monodispersed particles. Two aspects concerning with the template effects of the ordered latex film were emphasized: the polymeric spheres may result in orderly packed holes after calcination, and the dielectric interfacial layer surrounding the polymeric spheres may induce the formation of monodispersed silicate spheres with ordered stacking. Both aspects played important roles in the formation of the highly ordered inorganic porous materials by calcination the gel at high temperature. A method for preparing 3D ordered macroporous silicate materials was developed by using the ordered stacking structure of monodispersed polystyrene latex as a template. By using a modified sol | gel procedure, the ordered template was permeated and filled with silicate, and the title porous materials was formed after removing the template by calcination at high temperature. Moreover, the pores were highly ordered throughout all the sample. After observing the morphological profile of the sample before calcination, it was found that silicate existed in two typical morphologies: monodispersed particles in the cavities and interconnected network within the interstice of the template. The transition morphology was rod | like formed by the condensation of the silicate monodispersed particles. Two aspects concerning the template effects of the ordered latex film were emphasized: the polymeric spheres may result in orderly packed holes after calcination, and the dielectric interfacial l ayer surrounding the polymeric spheres may induce the formation of monodispersed silicate spheres with ordered stacking. both sides played important roles in the formation of the highly ordered inorganic porous materials by calcination the gel at high temperature.