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The silica opal templates were prepared from three silica colloids of different diameters of 230 nm,500nm and 1.5 μm by a filtration route.The large-scale stable opal template membranes after sintering the deposited SiO2 opal template can be successfully obtained by optimizing the pH value and NaCl concentration in silica colloidal solutions.The three-dimensionally ordered macroporous(3DOM) polyimide membranes without crack were fabricated by reproducing the structure of silica opal template.We prepared the pore-filling composite proton exchange membranes by filling the 3DOM structure with proton conducting organosilane sol.The result indicates that the composite membranes exhibit higher water uptake than pure filling organosilane gel.The proton conductivity increased with the increasing of pore cell in composite membranes.