Three-dimensional (3D) cubic ordered macroporous (140 nm) and binary macroporous (140, 80 nm) silica structures with ordered mesoporous (7.7 nm) walls have been synthesized by using cubic closed-packing colloidal crystals as templates. The colloidal crystals can be made from equal-sized or binary-sized latex spheres by the simple methods of self-sedimentation on the film or pressing into a pellet.