Abstract: Silica opals and multilayer heterostructures were fabricated by vertical deposition technique. Polystyrene inverse opals and gradient porous structures were obtained by colloidal templating, in order to control the pore microstructure of polymer porous materials. As shown in the scanning electron microscopy images, the polystyrene porous structures are precise replicas of inverse structures of the original templates. After being infiltrated with the polystyrene, the photonic stopband position of the opal composite is redshifted compared with the original template, and it is blueshifted after the opal template being removed. The filling ratio of polystyrene was calculated according to the Bragg formula．