Three-dimensional porous ordered SnO2 nanostructures have been fabricated by templating a sol–gel pre- cursor solution against the polystyrene nanospheres for the first time. Field emission scanning electron micrography (FESEM) indicates that the surface of the nanostructures is highly regular and the porous structures are perfectly ordered. Besides a broad emission band at 600 nm, the porous SnO2 nanostructures show an additional emission band at 430 nm, which is seldom seen in the bulk SnO2 materials. Spectral examinations and analyses reveal that the 430 nm band is induced by the interfacial effects between the porous frameworks.