We investigated the structural and optical properties of microporous titanium oxide (TiO2) fabricated by the sol-gel method using templates of colloidal crystals with polystyrene spheres when the annealing temperature was changed between 600 degrees and 1000 degrees C. From X-ray diffraction patterns and SEM images, the rutile TiO2 annealed at a high temperature did not form periodic porous bodies, while the anatase TiO2 annealed at lower than 800 degrees C formed periodic porous bodies. The porous TiO2 obtained acts as an air-sphere/TiO2 photonic crystal with an FCC structure. It is suggested that TiO2 sol annealed at a lower temperature do not lead to phase transition from the anatase phase to the rutile phase to obtain the air-sphere/TiO2 photonic crystal by the sol-gel method using templates of colloidal crystals.