Colloidal crystal-templating methods have been used to prepare inverse opal photonic crystals of silica, mercaptopropyl-functionalized silica, titania, and zirconia. Ordered arrays of uniformly sized polymer spheres were infiltrated with fluid precursors capable of condensation or crystallization. After solidification of the material in the void spaces between the spheres, the polymer templates were removed by calcination or solvent extraction, leaving inverse replicas of the template arrays. By carefully controlling the synthetic procedures, gram-scale quantities of powdered macroporous materials exhibiting photonic crystal properties were obtained. For materials with crystalline walls (titania and zirconia), this required minimization of the size of the nanocrystalline grains. Because the periodicity introduced into the wall structure by the colloidal crystal templates was on the order of optical wavelengths, Bragg diffractions from the planes produced photonic stop bands in the visible spectra of these materials. The stop bands were manifested as brightly colored reflections and an optical filtering behavior of the materials. A crystallographic indexing of the optical spectrum of a polycrystalline inverse opal confirmed the fcc ordering of the pores. The optical properties of these materials were modified in predictable manners by numerous methods, including tailoring the pore size, filling the pores with fluids of various refractive indices, and changing the compositions of the solid material. The wavelengths of the colorful reflections (stop bands) were found to be proportional to the pore size and to vary linearly with the refractive index of the fluid filling the pores. The physical and synthetic modifications reported here allowed for the preparation of powders with optical reflections and bright colors spanning the entire visible spectrum.