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Highly ordered and periodic mesoporous Nafion membranes with controlled structural symmetries including 2D hexagonal (2D-H),3D face-centered (3D-FC),3D cubic-bicontinuous (3D-CB) and 3D body-centered (3D-BC) have been successfully synthesized by a novel silica colloidal mediated self-assembly method.Among them,2D-H and 3D-CB structured Nafion possesses the highest proton conductivities,reaching 0.051 S cm-1,4 times better than 0.013 S cm-1 of pristine Nafion 112 under conditions of 40%RH and 80oC.The present study demonstrates that silica colloidal mediated self-assembly is a powerful technique to fabricate Nafion proton exchange membranes with highly ordered and controlled structural symmetries especially for fuel cells operated in low humidity conditions.