Titania, zirconia, and alumina samples with periodic three-dimensional arrays of macropores were synthesized from the corresponding metal alkoxides, using latex spheres as templates. In a fast, single-step reaction, the monomeric alkoxide precursors permeate the array of bulk polystyrene spheres and condense in air at room temperature. Close packed, open-pore structures with 320- to 360-nanometer voids are obtained after calcination of the organic component at 575 degreesC. The examples presented demonstrate the compositional diversity possible with this technique. The resulting highly structured ceramics could have applications in areas ranging from quantum electronics to photocatalysis to battery materials.