Facile and effective approaches were developed to fabricate 3D-ordered films of titania hollow spheres with different sphere diameters. The shell thickness of the sphere was adjusted in the range of 20-40 nm by changing the casting cycle of the titania precursor. The photonic stop band was observed for the 3D-ordered film and was tunable by the sphere diameter and the shell thickness. The stop band shifted from 930 to 547 nm. Crystal violet dye adsorbed on the film exhibited more than two times higher absorbance than that on a reference film of a flat titania layer, probably due to the red edge effect of the stop band and/or to the multiple scattering effect. The enhanced absorbance led to more efficient photodegradation of the dye under visible light and under solar light irradiation. A maximum photocatalytic enhancement of 22% is achieved. Finally, the influence of TiO2 morphology on photocatalytic activity was discussed. Compared with flat titania films, the existence of ordered macropores in titania spheres causes the stop band and a longer optical path due to multiple scattering. Both the red edge of the stop band and multiple scattering effects enhance the absorption of the dye, which results in the photocatalytic enhancement.