The ordered colloidal crystals were prepared by sedimentation of a solution of silica colloidal spheres of 298nm. Colloidal crystals were obtained after evaporation at 50°Cfor eight days while solution evaporates. These colloidal crystals were used to be templates and MMA was filled in the gap of silica spheres. SiO2/PMMA structures with a overlayer of PMMA were obtained by polymerization reaction carried out at 80°C for 24 h. After etched with the hydrofluoric acid (HF) for 24h, a piece of bluish violet film can be obtained. The film is flexible and free-standing and is enough tough to be curled to various shape. This kind of film can extend the usage of macroporous structures and have various potential applications in flexible photoelectronic device.