Three-dimensionally ordered macroporous polystyrene was successfully synthesized through using silica sphere colloid crystals as template and in-situ polymeriza tion of styrene inside the template. The silica spheres with a diameter of 330 n m and 2.75% relative standard deviation were prepared by seeding method. For th e purpose of improving the wetting ability between the silica particles and styr ene, the hydrophilic surface of silica particles was switched to hydrophobic by 3-Aminopropyl-triethoxysilan (APS). Three-dimensionally ordered colloidal crystal was prepared by assembling the modified particles through a vertical depositio n technique at 30℃ for 48h. Styrene monomer was filled into the void of the tem plate and the polymerization of the styrene was carried out at 60℃ for 6h, being used (put the initiator in here) as initiator. The three-dimensionally ordered macroporous polystyrene was thus obtained by removing the silica template from polystyrene materials with 04% HF. The macroporous polystyrene shows a beautif ul iridescence in reflected light, which resulted from Bragg diffraction. SEM im ages indicated that the pores with a diameter of about 210nm were arrayed period ically and connected with each other.