The fabrication of polymeric materials with ordered submicron-sized void structures is potentially valuable for many separation technologies as well as for emerging optical applications. This paper reports the preparation of macroporous polymer membranes with regular voids and the characterization of their diffractive optical properties. These materials are made using a colloidal crystal template of silica microspheres: the air between the spheres can be replaced by monomers that can be subsequently polymerized. The use of silica microspheres as templates makes it possible to employ chemical rather than thermal methods for template removal. For this reason, polymers as diverse as polyurethane and polystyrene can be used to create free-standing macroporous films, with thickness ranging from 0.5 to 50 mu m. Scanning electron microscopy of these samples indicates a well-formed porous structure consisting of voids ranging in diameter from 200 to 400 nm. These large cavities are not isolated, but rather interconnected by a network of monodisperse smaller pores (d = 50-130 nm) whose size can be controlled by varying the polymerization temperature. These membranes exhibit striking optical properties due to the periodic arrangement of air spheres in the polymer medium. Normal-incidence transmission measurements of these samples are compared to a theoretical model based on a scalar wave approximation. This model assumes an ordered structure of close-packed, three-dimensional air spheres. The good agreement between theory and experiment provides additional evidence of the long-range order of these samples.